Mass sensor and mass sensing method

ABSTRACT

A mass sensor in which a connection plate and a diaphragm are joined together at their respective sides; a sensing plate is joined to the connection plate at their respective sides in the direction perpendicular to the direction where the diaphragm is joined to the connection plate; a piezoelectric element consisting of a piezoelectric film and an electrode is installed on at least either one of plate surfaces of the sensing plate; and a resonating portion consisting of the diaphragm, the sensing plate, the connection plate, and the piezoelectric element is joined to a sensor substrate. Change in the mass of the diaphragm is measured by measuring change in the resonant frequency of the resonating portion accompanying the change in the mass of the diaphragm.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 10/465,470,filed Jun. 19, 2003, now allowed, which is a division of U.S.application Ser. No. 10/071,019, filed Feb. 8, 2002, now U.S. Pat. No.6,612,190, which is a division of U.S. application Ser. No. 09/297,655,filed May 4, 1999, now U.S. Pat. No. 6,386,053, which was the NationalStage of International Application No. PCT/JP98/03969, filed Sep. 4,1998, the entireties of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a mass sensor for determining a minutemass of a nanogram (10 ⁻⁹ g) order, for example, a mass sensor forsensing microorganisms such as bacteria, viruses, and protozoa (immunesensor), and a mass sensor for sensing moisture, toxic substances, orspecific chemical substances such as taste components (moisture meter,gas sensor, and taste sensor), and a method for sensing a mass. Inparticular, the present invention relates to a mass sensor, and a methodfor sensing a mass, conveniently used for determining the mass of a bodyto be sensed by measuring change in resonant frequencies caused bychanges in the mass of the diaphragm on which a catching substance forcatching a body to be sensed by reacting only with the body to be sensedis applied.

Since the mass sensor of the present invention is not limited to themeasurement of change in the mass of the catching substance applied on adiaphragm as described above, that is, not limited to the indirectmeasurement of change in the mass of a diaphragm, but it is naturallypossible to sense change in resonant frequency due to change in the massof the diaphragm itself, the mass sensor can also be used as a thicknessmeter for vapor-deposited films or a dew point meter.

Furthermore, even if the mass of the diaphragm is not changed directlyor indirectly, the mass sensor of the present invention can also be usedas a vacuum meter, a viscosity meter, or a temperature sensor by placingit in an environment to cause change in resonant frequency, that is, byplacing it in an environment of medium gases or liquids having differentdegrees of vacuum, viscosity, or temperature.

Thus, although the mass sensor of the present invention can be used invarious applications depending on its embodiments, the same basicprinciple is also applied to the measurement of change in resonantfrequencies of the diaphragm and the resonating portion including thediaphragm.

BACKGROUND OF THE INVENTION

Recent progress of scientific and medical technologies, and newlydeveloped medicines such as antibiotics and chemicals have enabled thetreatment of various diseases heretofore considered to be difficult totreat. On the other hand, especially in developed countries where peopleare accustomed in such medical civilization, immunological resistance ofhuman beings have lowered, and many people have suffered from variousdiseases caused by substances or microorganisms which heretofore had nothurt human beings.

Among what are referred to as diseases, microorganism examinations areessential for the treatment of diseases caused by microorganisms such asbacteria, viruses, or protozoa, to find their pathogens, to clarifytheir types, and to determine drugs to which they are sensitive.

At present, in the first stage of microorganism examinations, since thecause of a disease and the type of the pathogen can be estimated fromthe symptoms, various specimens, such as blood, are selected dependingon the type of the disease, pathogens present in the specimens aremorphologically identified, or antigens or the specific metabolites ofpathogens (e.g., toxins or enzymes, etc.) existing in the specimens areimmunochemically identified. This process is smear, tinction, ormicroscopy used in bacterial examinations, and in recent years,instantaneous identification has become possible in this stage byfluorescent antibody tinction or enzymatic antibody tinction.

Furthermore, the virus serological test, recently used in the detectionof viruses, is a method for proving the presence of specific immunityantibodies that appear in the serum of a patient. Examples of the methodinclude the complement fixation reaction in which the presence ofantibodies or antigens is determined by adding complements to testblood, and by observing whether the complements react with antigens orantibodies in the blood and fix to the cell membranes of the antigens orantibodies, or destroy the cell membranes.

Except extremely special cases where symptoms have not been seenheretofore, and the disease is caused by a new pathogen which has notbeen discovered, in the treatment of diseases caused by microorganismsor the like, adequate treatment can be conducted by finding pathogens inan early stage through the microorganism test described above, and thepatient can be led to recovery without worsening of the symptoms.

However, with methods such as smear, tinction, and microscopy, thedetection of microorganisms is often difficult depending on theirquantities, and time-consuming treatment such as the culture ofspecimens on an agar is required at need. Also in the virus serologicaltest, since measurements must be performed as a rule during both theacute stage and the convalescent stage for determination from themovement of the quantities of antibodies, there is the problem of timeconsumption from the point of view of prompt diagnosis.

As seen in complement fixation described above, when a substance to besensed reacts with a catching substance which catches the substance tobe sensed by reacting only with specific substance to be sensed,microorganisms, the mass of the catching substance increases by the massof the substance to be sensed, even slightly. Such an increase in themass similarly occurs in the relationship between a catching substanceand a chemical substance such as a specific gaseous substance and asmell component, and also applies to the case where a substrate itselfwithout change in the mass is a catching substance, on which a specificsubstance is deposited or added. On the contrary, when a reaction inwhich a substance to be sensed caught by a catching substance or thelike is released occurs, the mass of the catching substance or the likeslightly decreases.

As an example of a method for sensing change in such a small mass, U.S.Pat. No. 4,789,804 discloses in FIG. 27 thereof a mass sensor 80comprising a quartz oscillator 81 and electrodes 82, 83 facing thequartz oscillator. When any substance adheres externally on theseelectrodes 82, 83, the mass sensor 80 senses change in their mass usingchange in the resonant frequency of the thickness slip oscillation ofthe quartz oscillator 81 in the direction of the surface of theelectrodes. Since such a mass sensor 80 measures change in resonantfrequency basically caused by change in the mass load on the quartzoscillator 81, such a mass sensor 80 is considered to be able to be usedalso as a thickness meter for measuring the thickness or the growth of avapor-deposited film, or a moisture meter.

However, when such a quartz oscillator 81 is used, since the part onwhich an external substance adheres and the part for detecting resonantfrequency are in the same location, for example, the resonant frequencyis unstable when the piezoelectric properties of the mass sensor 80itself vary due to the temperature of the specimen or change intemperature. Also, if the specimen is a conductive solution, and whenthe mass sensor 80 is immersed unprotected in the specimen, ashort-circuit between electrodes may occur. Therefore, the mass sensor80 must be subjected to insulation such as resin coating.

SUMMARY OF THE INVENTION

The present invention aims to solve the above problems of a micro-masssensor, and according to the present invention, there are provided firstto sixth mass sensors described below.

As a first mass sensor, there is provided a mass sensor characterized inthat a piezoelectric element is arranged on at least a part of at leastone plate surface of a sensing plate, a side of at least one sheet-likediaphragm is joined to a side of said sensing plate so that the platesurface of said diaphragm is perpendicular to the plate surface of saidsensing plate, the other side of said sensing plate is joined to asensor substrate, and a resonance portion is formed of said sensingplate, said diaphragm, and said piezoelectric element.

Furthermore, as a second mass sensor, there is provided a mass sensorcharacterized in that a connection plate is joined to a diaphragm atrespective sides, a sensing plate is joined to said connection plate atrespective sides in the direction perpendicular to the joining directionof said diaphragm and said connection plate, a piezoelectric element isarranged on at least a part of at least one of the plate surfaces ofsaid sensing plate, at least a part of sides of said connection plateand said sensing plate is joined to a side of the sensor substrate, anda resonance portion is formed of said diaphragm, said connection plate,said sensing plate, and said piezoelectric element.

Furthermore, as a third mass sensor, there is provided a mass sensorcharacterized in that a connection plate is joined to a diaphragm atrespective sides, two sensing plates are joined to said connection plateat respective sides in the direction perpendicular to the joiningdirection of said diaphragm and said connection plate so as to sandwichsaid connection plate, a piezoelectric element is arranged on at least apart of at least one of the plate surfaces of at least one of saidsensing plates, at least a part of sides of said connection plate andsaid sensing plates is joined to a side of the sensor substrate, and aresonance portion is formed of said diaphragm, said connection plate,said sensing plates, and said piezoelectric element.

Here, in the third mass sensor, it is preferable that said piezoelectricelement is arranged on at least one of the plate surfaces of one of saidrespective sensing plates facing to each other via the connectionplates, and one or more, preferably a plurality of, slits are formed onthe other sensing plate in the direction perpendicular to the joiningdirection of said other sensing plate and said connection plate. It isalso preferable that respective piezoelectric elements are arranged onthe plate surfaces of said respective sensing plates facing to eachother via the connection plates in at least the same direction, and thatthe polarizing direction of the piezoelectric film in said piezoelectricelements arranged on one of the sensing plates, and the polarizingdirection of the piezoelectric film in said piezoelectric elementsarranged on the other sensing plate are opposite to each other withrespect to the connection plates.

Next as a fourth mass sensor, there is provided a mass sensorcharacterized in that a connection plate and a sensing plate notdirectly joined to each other are joined to said diaphragm at respectivesides so that the joining directions with the diaphragm are parallel toeach other, said connection plate and said sensing plate are joined toone side of a sensor substrate, a piezoelectric element is arranged onat least a part of at least one of the plate surfaces of said sensingplate, and a resonance portion is formed of said diaphragm, saidconnection plate, said sensing plate, and said piezoelectric element.

As a fifth mass sensor, there is provided a mass sensor characterized inthat an assembly of a diaphragm sandwiched with two connection plates byjoining at respective sides is placed across the side surfaces of adepression formed on a sensor substrate, each of two sensing plates isplaced across said connection plate and across the bottom side of saiddepression in the direction perpendicular to the direction of saidrespective connection plates sandwiching said diaphragm, a piezoelectricelement is arranged on at least a part of at least one of the platesurfaces of said sensing plates, and a resonance portion is formed ofsaid diaphragm, said connection plate, said sensing plates, and saidpiezoelectric element.

Here, a depression means that formed from sides facing to each other andthe bottom side connecting such sides; however, in the presentinvention, the bottom side is not necessarily a plane, but the shape ofthe bottom side may be changed variously unless the measurement of theoscillation and the resonant frequency of the diaphragm, such as theprovision of a depression or a projection in the bottom side, isaffected.

As a sixth mass sensor, there is provided a mass sensor characterized inthat an assembly of a diaphragm sandwiched with two connection plates byjoining at respective sides is placed across a through-hole formed on asensor substrate, at least a plurality of sensing plates are placedbetween said respective connection plates and the side of saidthrough-hole, or said diaphragm and the side of said through-hole, inthe direction perpendicular to the direction of said respectiveconnection plates sandwiching said diaphragm, a piezoelectric element isarranged on at least a part of at least one of the plate surfaces of atleast one of said sensing plates, and a resonance portion is formed ofsaid diaphragm, said connection plates, said sensing plates, and saidpiezoelectric element.

Here, in the sixth mass sensor, when the piezoelectric element isarranged on at least one of the plate surfaces in each pair of saidrespective sensing plates facing to each other via the connection platesor the diaphragm, it is preferable that one or more, preferably aplurality of, slits are formed on the other sensing plate in thedirection perpendicular to the joining direction of said other sensingplate and said respective connection plates. Also, when respectivepiezoelectric elements are arranged on the plate surface of each pair ofsaid respective sensing plates facing to each other via the connectionplates or the diaphragm in at least the same direction, it is preferablethat the polarizing direction of the piezoelectric film in saidpiezoelectric elements arranged on one of the sensing plates, and thepolarizing direction of the piezoelectric film in said piezoelectricelements arranged on the other sensing plate is opposite to each otherwith respect to the connection plates or the diaphragm.

In these second through sixth mass sensors, it is preferable that thediaphragm, the connection plate, and the sensing plate form a same planewhen joined to each other, that is, these members have almost the samethickness. It is also preferable that the sensing plate is fitted in andjoined to the depression formed by the connection plate and the sensorsubstrate. It is preferable for this that the diaphragm, the connectionplate, and the sensing plate are integrally formed from a diaphragm, andthe sensor substrate is laminated integrally with the diaphragm and thebase plate.

It is also preferable that a spring plate is bonded to one of or each ofplate surfaces of the connection plate, and this spring plate is joinedto the sensor substrate or the spring plate reinforcement. At this time,unlike the structure bonded using adhesives, it is preferable that thespring plate is integrally formed with an intermediate plate integrallyinserted between the diaphragm and the base plate, or integrally formedwith the spring plate reinforcement integrally formed with thediaphragm, and also integrally formed with the connection plate. When aplurality of connection plates are used, it is preferable that theassemblies of the connection plate and the spring plate have the sameshape. It is also preferable that the mass sensor has a reinforcingplate joined to the side of said sensor substrate, and in this case, itis preferable that the reinforcing plate is integrally formed with thespring plate and the sensor substrate.

Since a catching substance reacting only with a substance to be sensedand catching the substance to be sensed is applied on the diaphragm, thepiezoelectric element measures change in the resonant frequency of theresonating portion in the state when the substance to be sensed has notbeen caught by the catching substance, and in the state after thesubstance to be sensed has been caught by said catching substance, allthe mass sensors according to the present invention are suitably used inapplications to measure the mass of the substance to be sensed caught bythe catching substance.

It is preferable that at least two resonating portions are placed on thesensor substrate, and the catching substance is not applied to one ofthe diaphragm of the resonating portions to use this diaphragm forreferencing. On the other hand, it is also preferable that differentcatching substances are applied to each resonating portion, that is, aplurality of resonating portions to which more than one of differentcatching substances are separately applied are provided in a sensor.Here, more than one resonating portion may be placed on the sensorsubstrate so as to expand the dynamic range by integrating the signalsfrom the respective resonating portions. Also, a through-hole of anoptional shape may be formed inside said sensor substrate, and theresonating portion may be formed on the internal circumferential surfaceof the through-hole.

It is also preferable, to improve sensitivity, that one of thepiezoelectric element is split into two portions; one is used fordriving and the other is used for sensing. Furthermore, it ispreferable, to improve sensitivity, that two piezoelectric elements areplaced on one resonating portion, and one of the piezoelectric elementsis used for driving and the other is used for sensing. Therefore, eachof the two piezoelectric elements placed on a resonating portion may befurther split into two portions, and in this case, each of the twopiezoelectric elements has both driving and sensing functions.

Furthermore, when the specimen is a conductive solution, it ispreferable to provide a position sensor consisting of a pair ofelectrodes on the middle between the diaphragm and the piezoelectricelement on the sensor substrate, so that the diaphragm is immersed inthe solution but the piezoelectric element is not immersed in thesolution even if the mass sensor is immersed, so as to install the masssensor on a suitable position. Even if the specimen is a conductivesolution, the electrodes or other parts can be prevented fromshort-circuiting, if the piezoelectric element, the electrodes of thepiezoelectric element and electrode leads connected to the electrode,are coated with a resin or glass insulation coating layer. Furthermore,it is preferable that a shield layer consisting of a conductive materialis formed on the surface of said insulation coating layer, so as toreduce noise such as external electromagnetic waves.

It is preferable that the sensor substrate, diaphragm, connection plate,sensing plate, and spring plate constituting a mass sensor of thepresent invention are integrally composed of stabilized zirconia orpartially stabilized zirconia. As the material for the piezoelectricfilm in the piezoelectric element, a material containing a componentmainly consisting of lead zirconate, lead titanate, and lead magnesiumniobate is suitably used, oscillation modes, adjusting the resonantfrequencies and sensitivity can be controlled if the shapes of thediaphragm, connection plate, sensing plate, or spring plate aredimensionally adjusted by trimming with laser processing or machining.It is further preferable that the electrode of the piezoelectric elementis laser-processed or machined to adjust the effective electrode area ofthe piezoelectric element.

The term “piezoelectric” used herein includes piezoelectricity andelectric distortion, and what are referred to as a piezoelectric elementinclude electric distortion elements, and piezoelectric ceramics includeelectric distortion ceramics.

Next, according to the present invention, methods for mass sensingcorresponding to the structure of various mass sensors as describedabove are provided. First, there is provided a method for sensing themass with the mass sensor in which a side of at least one sheet-likediaphragm is joined to a side of said sensing plate so that the platesurface of said diaphragm is perpendicular to the plate surface of saidsensing plate on which a piezoelectric element is installed, and theother side of said sensing plate is joined to the sensor substrate,characterized in measuring with said piezoelectric element resonantfrequency on the basis of at least either one of, θ-mode swingoscillation of said diaphragm in which said diaphragm makespendulum-like oscillation centered on the perpendicular axisperpendicularly passing through the center of a fixed plane, which isthe joining surface of said diaphragm and said sensing plate, in thedirection perpendicular to the side of said diaphragm and alsoperpendicular to said perpendicular axis, the φ-mode swing oscillationof said diaphragm in which said diaphragm makes pendulum-likeoscillation centered on said perpendicular axis with the swing in thedirection perpendicular to the side of said diaphragm and alsoperpendicular to said perpendicular axis accompanied by the swing in thedirection parallel to the side of said diaphragm, or the oscillation ofsaid diaphragm in the direction of said perpendicular axis.

Such a method for mass sensing with a mass sensor is suitably adopted asa method for mass sensing using the first mass sensor according to thepresent invention as described above from its structure.

Also, according to the present invention there is provided a method forsensing the mass with the mass sensor having at least one piezoelectricelement, in which a connection plate is joined to a diaphragm atrespective sides, at least one sensing plate is joined to saidconnection plate at respective sides in the direction perpendicular tothe joining direction of said diaphragm and said connection plate, andat least a part of sides of said connection plate and said sensing plateis joined to a part of sides of the sensor substrate, characterized inmeasuring with said piezoelectric element resonant frequency on thebasis of at least either one of, the θ-mode swing oscillation of saiddiaphragm in which said diaphragm makes pendulum-like oscillationcentered on the perpendicular axis perpendicularly passing through thecenter of a fixed plane, which is the joining surface of said connectionplate and said sensor substrate, in the direction perpendicular to theside of said diaphragm and also perpendicular to said perpendicularaxis, or the φ-mode swing oscillation of said diaphragm in which saiddiaphragm makes pendulum-like oscillation centered on said perpendicularaxis with the swing in the direction perpendicular to the side of saiddiaphragm and also perpendicular to said perpendicular axis accompaniedby the swing in the direction parallel to the side of said diaphragm.

Such a method for mass sensing with a mass sensor is suitably adopted asa method for mass sensing using the second and third mass sensorsaccording to the present invention as described above from theirstructures.

Furthermore, according to the present invention there is provided amethod for sensing the mass with the mass sensor having at least onepiezoelectric element, in which an assembly of a diaphragm sandwichedwith two connection plates by joining at respective sides is placedacross the side surfaces of a depression or across a through-hole formedon a sensor substrate, at least a plurality of sensing plates are placedbetween said respective connection plates and the bottom side of saiddepression or the side of said through-hole, or between said diaphragmand the bottom side of said depression or the side of said through-hole,in the direction perpendicular to the direction of said respectiveconnection plates sandwiching said diaphragm, characterized in measuringwith said piezoelectric element resonant frequency on the basis of atleast either one of, the θ-mode swing oscillation of said diaphragm inwhich said diaphragm makes pendulum-like oscillation centered on theperpendicular axis perpendicularly passing through the center of a fixedplane, which is the joining surface of said connection plate and saidsensor substrate, in the direction perpendicular to the side of saiddiaphragm and also perpendicular to said perpendicular axis, the φ-modeswing oscillation of said diaphragm in which said diaphragm makespendulum-like oscillation centered on said perpendicular axis with theswing in the direction perpendicular to the side of said diaphragm andalso perpendicular to said perpendicular axis accompanied by the swingin the direction parallel to the side of said diaphragm, the swingoscillation of said diaphragm centered on said perpendicular axis,oscillating in parallel to the direction perpendicular to the side ofsaid diaphragm and also perpendicular to said perpendicular axis, or therotating oscillation of said diaphragm in the plate surface of saiddiaphragm.

Such a method for mass sensing with a mass sensor is suitably adopted asa method for mass sensing using the fifth and sixth mass sensorsaccording to the present invention as described above from theirstructures, and also suitably adopted as a method for mass sensing usingthe fourth mass sensor having a structure in which the sensing platealso functions as the connection plate.

According to a mass sensor of the present invention, as described above,change in a minute mass occurring in a diaphragm can be known accuratelyin a short time from a specific value of change in the resonantfrequencies of the resonating portion provided in the mass sensor, andthe mass sensor has an advantage of easy measuring operation. Therefore,by placing the mass sensor in an environment changing the resonantfrequencies of the resonating portion, various physical and chemicalquantities can be measured. For example, the mass sensor of the presentinvention can be used suitably as a thickness meter for vapor-depositedfilms and a dew point meter; which utilize direct change in the mass ofthe diaphragm, a vacuum meter, viscosity meter, and temperature sensor,which utilize the environment where the diaphragm is placed, such asvacuum, viscosity, and temperature; and especially, for theidentification of a substance to be sensed and the measurement of itsmass by applying to the diaphragm a catching substance which selectivelyreacts with the substance to be sensed such as a microorganism or achemical substance in a specimen, and by utilizing change in the mass ofsuch a catching substance.

BRIEF DESCRIPTION OF THE DRAWINGS

For a fully understanding of the nature and objects of the invention,reference should be made to the following detailed description of apreferred mode of practicing the invention, read in connection with theaccompanying drawings in which:

FIGS. 1(a)-(d) are perspective views showing an embodiment of a masssensor of the present invention; and (a) through (d) are perspectiveviews of the embodiments in which the location and the number ofdiaphragms are changed;

FIG. 2 is a perspective view showing an embodiment of a piezoelectricelement installed in a mass sensor of the present invention;

FIG. 3 is a perspective view showing an embodiment of anotherpiezoelectric element installed in a mass sensor of the presentinvention;

FIG. 4 is a perspective view showing an embodiment of still anotherpiezoelectric element installed in a mass sensor of the presentinvention;

FIGS. 5(a)-(c) are diagrams showing another embodiment of a mass sensorof the present invention; (a) is a plan; (b) is a diagram illustrating aθ-mode swing oscillation; and (c) is a diagram illustrating a φ-modeswing oscillation;

FIG. 6 is a plan showing still another embodiment of a mass sensor ofthe present invention;

FIGS. 7(a)-(e) are diagrams showing still another embodiment of a masssensor of the present invention; (a) is a plan; and (b) through (e) aresectional views;

FIGS. 8(a)-(b) are diagrams illustrating the driving of a mass sensor ofthe present invention;

FIGS. 9(a)-(c) are diagrams showing still another embodiment of a masssensor of the present invention; (a) and (b) are plans; and (c) is asectional view;

FIGS. 10(a)-(d) are plan views showing still another embodiment of amass sensor of the present invention;

FIG. 11 is a plan showing the appearance of still another embodiment ofa mass sensor of the present invention;

FIG. 12 is a plan showing the structure of the sensor portion in themass sensor shown in FIG. 11;

FIG. 13 is a perspective view showing the structure of the sensorportion in the mass sensor shown in FIG. 12;

FIG. 14 is another perspective view showing the structure of the sensorportion in the mass sensor shown in FIG. 12;

FIG. 15 is a plan showing still another embodiment of a mass sensor ofthe present invention;

FIGS. 16(a)-(c) are plan views showing still another embodiment of amass sensor of the present invention;

FIGS. 17(a)-(b) are diagrams showing still another embodiment of a masssensor of the present invention; (a) is a plan; and (b) is a sectionalview;

FIG. 18 is a plan showing still another embodiment of a mass sensor ofthe present invention;

FIGS. 19(a)-(d) are diagrams showing still another embodiment of a masssensor of the present invention; (a) is a plan; and (b) through (d) aresectional views;

FIGS. 20(a)-(b) are plan views showing still another embodiment of amass sensor of the present invention;

FIGS. 21(a)-(c) are plan views showing still another embodiment of amass sensor of the present invention;

FIGS. 22(a)-(f) are diagrams showing still another embodiment of a masssensor of the present invention; (a) through (d) and (f) are plansshowing various structures in which a sensing plate is joined toconnection plates; and (e) is a plan showing a structure in which asensing plate is connected to a diaphragm;

FIG. 23 is a plan showing an example of processing a green sheet for asensor substrate used in the fabrication of a mass sensor of the presentinvention;

FIG. 24 is a diagram illustrating the size and shape which is preferablyadjusted on the fabrication of a mass sensor of the present invention;

FIG. 25 is a diagram illustrating an example of processing apiezoelectric element of a mass sensor of the present invention;

FIG. 26 is a diagram illustrating operation properties of a mass sensorof the present invention;

FIG. 27 is a sectional view illustrating the basic structure of aconventional micro-mass sensor; and

FIG. 28 is a perspective view showing the structure of a quartzoscillator of a conventional quartz friction vacuum meter.

DETAILED DESCRIPTION OF THE INVENTION

The embodiments of the present invention will be described belowreferring to the drawings, in particular focusing on a mass sensor usedby applying a catching substance that reacts only with a specificsubstance to be sensed and catches the specific substance to be sensedto the diaphragm.

However, since the present invention is used in many other applicationsas described above, the present invention is not in any way limited tothe embodiments described below.

FIG. 1(a) is a perspective view showing an embodiment of a mass sensor50A of the present invention. On the plate surface of at least onesensing plate 51 is provided a piezoelectric element 55 consisting of afirst electrode 52, a piezoelectric film 53, and a second electrode 54.The piezoelectric element 55 may be provided on both the surfaces of thesensing plate 51, and the first and second electrodes 52, 54 areconnected to an electrode lead (not shown) used for connecting them to afrequency meter or the like.

A sheet-like diaphragm 56 is joined to a side of the sensing plate 51 sothat the plate surface of the diaphragm 56 and the plate surface of thesensing plate 51 are perpendicular to each other. Here, “the sides ofthe sensing plate 51” means a plane perpendicular to the plate surfaceof the sensing plate 51 on which the piezoelectric element 55 isinstalled, that is, a plane in the thickness direction, and “a side”means one of the sides. Furthermore, the other side of the sensing plate51, here, the side opposite to the side to which the diaphragm 56 isjoined, is joined to a sensor substrate 49, and a resonating portion isformed of the diaphragm 56, the sensing plate 51, and the piezoelectricelement 55, to form the mass sensor 50A.

Here, a diaphragm mainly means the place to cause or to be subject tochange in mass, and is an element that oscillates in various modes asdescribed later; a connection plate means an element to connect thediaphragm, sensor substrate, and sensing plate; and a sensing platemeans an element that is deformed by the movement of the diaphragm, andtransmits the strain to the sensing element, such as a piezoelectricelement, installed on the surface, or on the contrary, transmits strainor oscillation generated by a driving element, such as a piezoelectricelement, to the diaphragm. The sensor substrate means an element tosupport the resonating portion, carry various electrode terminals forconnecting to measuring instruments, and is used for handling in actualuses.

Methods for using such a mass sensor 50A include, for example, a methodin which a catching substance that reacts with and catch only asubstance to be sensed is applied to the diaphragm 56, the diaphragm 56is immersed in a liquid specimen or exposed to a gaseous environmentsuch as a specific gas, to measure change in the resonant frequencies ofthe mass sensor 50A with the piezoelectric element 55, or a method inwhich the resonant frequency is measured after the diaphragm 56 isimmersed in a liquid specimen and dried in a gas. An example of such asubstance to be sensed is an antigen which causes a disease, and anexample of the catching substance is an antibody for such an antigen.

Here, the resonant frequency of the mass sensor 50A varies depending onthe mass of the resonating portion, in particular, the mass of thediaphragm 56. That is, the resonant frequency of the resonating portionin the state where the substance to be sensed has not been caught by thediaphragm 56 is different from the resonant frequency of the resonatingportion in the state where the substance to be sensed has been caught,depending on the mass of the substance to be sensed that has beencaught. Therefore, by measuring change in the resonant frequencies usingthe piezoelectric element 55, the mass of the substance to be sensedcaught by the catching substance applied on the diaphragm 56 can bemeasured.

In the same principle, the mass sensor 50A can be used for measuringdecrease in the mass, when the mass of the diaphragm 56 decreases fromthe mass in the initial state. For example, the mass sensor 50A can beused suitably when the catching substance applied is peeled off for somereason, when the extremely slight corrosion or an extremely small amountof dissolution in a specific solution of the material itself of thediaphragm 56 is to be checked, or for the purpose to measure change inthe mass of a specific chemical substance, other than the catchingsubstance, applied to the diaphragm 56 due to the evaporation ordissolution of such a chemical substance.

The structure of such a mass sensor 50A can be summarized to be astructure in which a side of at least one sheet-like diaphragm 56 isjoined to a side of a sensing plate 51 so that the plate surface of thediaphragm 56 is perpendicular to the plate surface on which thepiezoelectric element 55 of the sensing plate 51 is installed, and theother side of the sensing plate 51 is joined to the sensor substrate 49.Here, as the oscillation mode of the diaphragm used for measuringresonant frequency in the mass sensor 50A, it is preferable to measurethe resonant frequency of the resonating portion on the basis of atleast either one of oscillation among θ-mode swing oscillation(hereafter referred to as “θ-mode”) in which the diaphragm 56 performspendulum-like oscillation centered on the perpendicular axis (Y-axis)perpendicularly passing through the center of the fixed plane, which isthe plane where the diaphragm 56 is joined to the sensing plate 51 inFIG. 1(a), in the direction perpendicular to the side of the diaphragm56, and also in the direction perpendicular to the Y-axis, that is inthe direction of X-axis; φ-mode swing oscillation (hereafter referred toas “φ-mode”) in which the diaphragm 56 performs pendulum-likeoscillation centered on the Y-axis in the direction perpendicular to theside of the diaphragm 56, and also in the direction perpendicular to theY-axis, that is in the direction of X-axis, and accompanying swingenlarged in the direction parallel to the side of the diaphragm 56(Z-axis) as the diaphragm 56 travels apart from the Y-axis; andoscillation in the direction of the Y-axis.

These oscillation modes mean that the direction of the oscillation ofthe diaphragm 56 is dominant in the directions described above, but thedirectional components other than the above directions are notcompletely excluded. This applies also to the citation of oscillationmodes on describing various embodiments below.

Since these θ-mode and φ-mode are the same as those in the mass sensor30 described later, these will be described in detail in the descriptionof the mass sensor 30; however, since these oscillation modes are therigid body modes utilizing the side of the diaphragm 56, they aresuitably used particularly when the diaphragm 56 or the entire masssensor 50A is immersed in a liquid.

When the mass sensor 50A is used in a gas, the bending mode in whichbending in the direction of Z-axis in FIG. 1(a) is dominant can be alsoeffectively used in addition to the above oscillation modes. When thebending mode is used in a liquid, although the effect of the viscosityor density of the liquid is larger than in the above θ-mode and φ-mode,change in mass can be known by measuring resonant frequency. Thus, bydetecting voltage induced on the piezoelectric film 53 caused by theoscillation of the diaphragm 56 described above, change in the resonantfrequency, or change in the mass of the diaphragm 56 can be known.

Using the operation principle of the mass sensor 50A described above,those shown in FIGS. 1(b) through 1(d) can be exemplified as embodimentson mass sensors having similar function to the embodiment shown in FIG.1(a). The mass sensor 50B shown in FIG. 1(b) has two parallel diaphragms56 similar to the diaphragm 56 in the embodiment of FIG. 1(a) on a sideof the sensing plate 51. The use of a plurality of diaphragms 56 canimprove the dynamic range of the mass sensor.

The location where a plurality of diaphragms 56 are joined to thesensing plate 51 is not limited as far as it is a side other than theside where the sensing plate 51 is joined to the sensor substrate 49.Also, since at least one diaphragm 56 is required, the diaphragm 56 maybe joined to the side perpendicular to the side where the sensing plate51 is joined to the sensor substrate 49 among the sides of the sensingplate 51 as in the mass sensor 50C shown in FIG. 1(c). Furthermore, eachof two diaphragms 56 may be joined to a pair of sides opposite to eachother as in the mass sensor 50D shown in FIG. 1(d) to improve dynamicrange as in the mass sensor 50B.

At this time, it is preferable that the location where the diaphragm 56is joined to the sensing plate 51 is in the vicinity of the end of thesensing plate 51 apart from the sensor substrate 49 as much as possible,because the Q-value (peak value, hereafter referred to as “Q-value”) ofthe θ-mode and φ-mode can be increased, that is, the amplitude of thediaphragm 56 is increased, and the sensitivity is improved. Of course,the optional combination of these embodiments of mass sensors 50A-50Dshown in FIGS. 1(a) through 1(d) may also be used.

Although the piezoelectric element 55 installed on mass sensors 50A-50Ddescribed above is typically of a lamination type in which a firstelectrode 52, a piezoelectric film 53, and a second electrode 54 arelaminated as shown in FIG. 2, a piezoelectric element 62A having a combstructure in which a piezoelectric film 58 is placed on a sensing plate57 shown in FIG. 3, and a first electrode 59 and a second electrode 60form gaps 61 of a constant width on the top of the piezoelectric film 58can also be used. The first electrode 59 and the second electrode 60 inFIG. 3 may be formed in the surface between the sensing plate 57 and thepiezoelectric film 58. Furthermore, as shown in FIG. 4, a piezoelectricelement 62B in which a piezoelectric film 58 is buried between thecomb-shaped first and second electrodes 59, 60 is also suitably used.

Here, when a comb-shaped electrode as shown in FIG. 3 or 4 is used, themeasuring sensitivity can be raised by reducing the pitch 63. Suchpiezoelectric elements shown in FIGS. 2 through 4 are used in all themass sensors of the present invention described later.

Although the measurement of mass as described above can be performedusing mass sensors 50A through 50D, increase in detecting sensitivity islimited, because the area of the diaphragm 56 is inevitably small makingthe area to which a catching substance is applied small, and makingchange in mass small when the thickness of the vapor-deposited film ismeasured. Furthermore, warp or bend may occur on the diaphragm 56, andin addition, the mode in which only the diaphragm 56 oscillates maystrongly appear. Therefore, it is preferable to modify the structure tothat shown in FIG. 5(a) to solve such problems.

That is, FIG. 5(a) is a plan showing another embodiment of a mass sensorof the present invention. In the mass sensor 30, a diaphragm 31 and aconnection plate 33 are joined at their respective sides, and a sensingplate 32 is joined to the connection plate 33 at their respective sidesin the direction perpendicular to the Y-axis direction, which is thedirection where the diaphragm 31 and the connection plate 33 are joined,that is the X-axis direction. A piezoelectric element 35 is installed onat least a part of at least one of the plate surfaces of the sensingplate 32 to constitute a sensing portion 36, and at least a part of thesides of the connection plate 33 and the sensing plate 32 is joined tothe side of the sensor substrate 34, without the diaphragm 31 beingdirectly joined to the sensor substrate 34. Thus, a resonating portionis formed of the diaphragm 31, the connection plate 33, the sensingplate 32, and the piezoelectric element 35, to form a mass sensor 30.

Here, although the diaphragm 31, the connection plate 33, and thesensing plate 32 are not necessarily required to have the samethickness, preferably they have the same thickness so as to form thesame surface, and more preferably, they are integrally formed. Theconditions related to the thickness and joining for the diaphragm 31,the connection plate 33, and the sensing plate 32 are likewise appliedto all the mass sensors according to the present invention describedbelow. Furthermore, the sides of the connection plate 33 and the sensingplate 32 are preferably formed integrally with the sensor substrate 34.

The structure of such a mass sensor 30 can be summarized to be a masssensor having at least one piezoelectric element, in which a connectionplate 33 and a diaphragm 31 are joined together at their respectivesides; at least one sensing plate 32 is joined to the connection plate33 at their respective side in the direction perpendicular to thedirection where the diaphragm 31 is joined to the connection plate 33;and at least a part of the sides of the connection plate 33 and thesensing plate 32 is joined to a part of the sides of the sensorsubstrate 34. In the mass sensor 30, at least either one of oscillationmodes can be utilized among the bending mode in which the diaphragm 31oscillates as it bends in the direction of Z-axis (not shown)perpendicular to both X and Y axes; the axial rotation mode in which itoscillates as it rotates around the Y-axis; the θ-mode in which thediaphragm 31 performs pendulum-like oscillation centered on the Y-axiswithin the plate surface of the diaphragm 31 in the X-axis direction soas to make a constant angle θ to the Y-axis; and the φ-mode which ispendulum-like oscillation centered on the Y-axis in the X-axisdirection, and in which the swing component in the direction of theZ-axis (not shown) parallel to the side of the diaphragm 31 is increasedas it travels apart from the Y-axis.

Here, the above θ-mode and the φ-mode will be described in furtherdetail. FIG. 5(b) is a diagram illustrating the θ-mode, and shows changein the location of the diaphragm 31 when the mass sensor 30 of FIG. 5(a)is viewed from the A-A direction in FIG. 5(a), that is on the X-axisfrom the Y-axis direction. Here, the upper end surface 31F of thediaphragm 31 is on the location P1 when not oscillating, but in theθ-mode, the diaphragm 31 performs pendulum-like oscillation centered onthe Y-axis within the plate surface of the diaphragm 31, that is, in theX-Y axis plane in the X-axis direction so as to make a constant angle θto the Y-axis. At this time, in the A-A direction, the movement of theupper end surface 31F of the diaphragm 31 can be described as thereciprocal movement between locations P2 and P3 on the X-axis, and thisoscillating movement is defined as the θ-mode.

Next, FIG. 5(c) is a diagram illustrating the φ-mode, and similar toFIG. 5(b), FIG. 5(c) shows change in the location of the diaphragm 31viewed from the A-A direction shown in FIG. 5(a). Here also, the upperend surface 31F of the diaphragm 31 is on the location P1 when notoscillating. As described above, in the φ-mode, the diaphragm 31performs pendulum-like oscillation centered on the Y-axis within thesurface of the diaphragm 31 in the X-axis direction, and the swingcomponent in the direction of the Z-axis parallel to the side of thediaphragm 31 is increased as it travels apart from the Y-axis. That is,the movement of the upper end surface 31F of the diaphragm 31 in the A-Adirection can be described as the reciprocal movement between locationsP4 and P5 on the arc orbit S having the center O at a point of theZ-axis and passing through location P1. At this time, the angle made bythe Z-axis and the straight line connecting the diaphragm 31 and thecenter O is φ, and such an oscillation mode is defined as the φ-mode.

Due to these various modes of oscillation, the piezoelectric film of thepiezoelectric element 35 is subjected to stretching stress or flexuralstress, and a voltage corresponding to the magnitude of the stress isgenerated. The resonant frequency of the resonating portion comprisingthe diaphragm 31, the connection plate 33, and the sensing portion 36 atthis time is measured by the piezoelectric element 35. Now, since theresonant frequency of the resonating portion varies mainly accompanyingchange in the mass of the diaphragm 31, when some substance attaches to,or detaches from the diaphragm 31 to cause the mass of the diaphragm 31to change, the change in the mass can be obtained from change in theresonant frequencies of the resonating portion in the same principle asmass sensors 50A through 50D. The dynamic range can be increased byinstalling two piezoelectric elements 35 on both surfaces of the sensingplate 32, and by the comparison operation of the signals sensed by thesepiezoelectric elements 35. Furthermore, in this case, sensitivity can beimproved by using one of the piezoelectric elements 35 for driving(exciting) the diaphragm 31, and the other for sensing (oscillationreceiving).

Further in FIG. 5(a), it is preferable to improve sensitivity, toinstall one piezoelectric element 35 in the Y-axis direction split itinto two piezoelectric element parts 35A and 35B, and use these fordriving and sensing, respectively. The methods for splitting thepiezoelectric element 35 include a method in which after installing onepiezoelectric element 35, it is split by laser processing, and a methodto install two piezoelectric element parts 35A and 35B respectively inthe same time. These methods for installing a plurality of piezoelectricelements, and for splitting and using respective piezoelectric elements35 can be applied to all the mass sensors according to the presentinvention.

Now, when a resonant frequency is measured by immersing the diaphragm 31in a liquid utilizing the bending mode described above, the diaphragm 31has a disadvantage that the diaphragm 31 receives resistance from theliquid corresponding to the area of the diaphragm 31, and becomesdifficult to sense change in the minute mass of the diaphragm 31.However, when the specimen is gas, the bending mode can be used becausethe resistance value is small. In this case, however, it is preferableto shorten the length of the diaphragm 31 in Y-axis and X-axisdirections.

In the rotation mode around the Y-axis, since change in the mass of thediaphragm 31 where the width of the connection plate 33 (width in theX-axis direction) is extended toward the diaphragm 31, in the vicinityof the Y-axis little affects the rotational oscillation of the diaphragm31, and less contributes to the rotational oscillation than the samechange in mass at the left and right ends of the diaphragm 31, a problemarises in sensitivity depending on the location where change in mass ofthe diaphragm 31 occurs. In this case, measurement error can beminimized by making the shape of the diaphragm 31 concave, and makingthe area in the vicinity of the Y-axis small like the mass sensor 30A inFIG. 6. At this time, in order to minimize measurement error at thelocation of applying the specimen when change in mass is same, it ispreferable to decrease the dimension H₁; in order to raise the dynamicrange, it is preferable to increase the dimension H₂.

Whereas, when the θ-mode or the φ-mode is used, no matter which thespecimen is, liquid or gas, the effect of the location where thecatching substance is applied to the diaphragm 31 can be minimized bydecreasing dimensions H₃ and H₄ in FIG. 5. In addition, since thediaphragm 31 is thin, the effect of density or viscosity is small, andsince the diaphragm 31 is operated in a rigid body mode, it is littleaffected by temperature change, making the mass sensor excel insensitivity and environment resistance. Therefore, it is preferable tooperate the mass sensor of the present invention in the θ-mode or theφ-mode.

Next, in the present invention, a structure in which a spring plate isbonded in one plate surface or either surface of the connection plate,and the spring plate is joined to a sensor substrate or a spring platereinforcement can also be adopted favorably. FIG. 7(a) is a plan viewshowing the mass sensor 40A, which is an embodiment in which a springplate 38 and a spring plate reinforcement 39 are installed on the masssensor 30 described above. FIGS. 7(b) through (e) are various sectionalviews on the Y axis viewed from the X-axis direction, showing examplesof the installation of the spring plate 38 and the spring platereinforcement 39.

The spring plate 38 is joined to at least one plate surface of theconnection plate 33. Although the width of the spring plate 38 may benarrower than the width of the connection plate 33 as FIG. 7(a) shows,it is preferable that the width of the spring plate 38 is the same asthe width of the connection plate 33. Also, when spring plates 38 madeof the same material are bonded on both plate surfaces of the connectionplate 33, it is preferable that the shapes of these spring plates 38 arethe same. However, when the materials of the spring plates 38 arechanged on different materials of the connection plate 33, the shapes ofthese spring plates 38 are not required to be the same, but suitableshapes may be adopted considering the Young's modulus or other physicalproperties of each spring plate 38.

Such spring plates 38 are joined also to the sensor substrate 34 as arule. In this case, the necessity of the spring plate reinforcement 39is determined depending on the location where the connection plate 33 isjoined to the sensor substrate 34. That is, when the connection plate 33is joined to the location where the spring plate 38 is directly joinedto the sensor substrate 34 as shown in FIGS. 7(b) and (c), no springplate reinforcement 39 is required, because the sensor substrate 34 alsofunctions as the spring plate reinforcement 39. At this time, the springplate 38 may be bonded only on one plate surface of the connection plate33.

However, when the connection plate 33 is joined to the sensor substrate34 at its end as FIG. 7(d) shows, for the spring plate 38A, the sensorsubstrate 34 also functions as the spring plate reinforcement 39;however, for the spring plate 38B, it is preferable to provide a springplate reinforcement 39 for supporting the spring plate 38B. Even whenthe connection plate 33 is joined to the sensor substrate 12 at its endas FIG. 7(e) shows, no spring plate reinforcement 39 is required if onlythe spring plate 38A which can be joined to the sensor substrate 12 isbonded, and no spring plate 38B is used.

Thus, by bonding the spring plate 38, the mechanical strength of theresonating portion is enhanced. Also, by this, the thickness of theconnection plate 33 and the diaphragm 31 can be decreased, and theattenuation of the resonance peak on measurement in a liquid isadvantageously reduced. Furthermore, it is preferable to bond springplates 38 on both plate surfaces of the connection plate 33 because thecenter of gravity of the spring portion consisting of the connectionplate 33 and the spring plates 38 can be excited, and the diaphragm 31oscillates easily in the θ-mode, when exciting the diaphragm 31 with thepiezoelectric element 35.

Here, sectional views on the X-axis viewed from the Y-axis direction ofthe embodiments shown in FIGS. 7(c) and (d) are shown in FIGS. 8(a) and(b), respectively. In FIG. 8(a), since the piezoelectric element 35 candrive the center O of the spring plate 38A, the spring plate 38B, andthe connection plate 33 in the X-axis direction, the diaphragm 31 andthe whole resonating portion oscillate easily in the θ-mode in theX-axis direction. Whereas, in the case of FIG. 8(b), since the center Oof the spring plate 38A, the spring plate 38B, and the connection plate33 is not on the connection plate 33, the driving force in the X-axisdirection (arrow S₁) by the piezoelectric element 35 is exerted as arotational force around the center O (arrow S₂) and the rotation modeappears easily, even though the rotation mode is restricted by therigidity of the spring plate 38A itself.

When the spring plate 38 is used as described above, it is alsopreferable that a reinforcing plate 41 is bonded to the spring plate 38and joined to the side of the sensor substrate 34, as shown in the masssensor 40B of FIG. 9. FIGS. 9(a) and (b) are plans of the mass sensor40B viewed from the top and the bottom, respectively; and FIG. 9(c) is asectional view along the X-axis viewed from the Y-axis direction in FIG.9(b). Here, the reinforcing plate 41 is bonded to the spring plate 38Ainstalled on the connection plate 33, and joined to the sensor substrate34 at the perpendicularly cut side. Preferably, the reinforcing plate 41is integrally formed with the spring plate 38 and the sensor substrate34.

Since such a structure facilitates the diaphragm 31 to resonate in theθ-mode and the φ-mode, the attenuation of the Q value is reduced, andsensitivity is advantageously improved. Therefore, the structure issuitable particularly for measurement in liquid.

Obviously, the spring plate described above can be applied to all themass sensors according to the present invention in which a connectionplate is used as a component, and it is preferable that the spring plateis integrally formed with an intermediate plate integrally insertedbetween the diaphragm plate and the base plate, or integrally formedwith a spring plate reinforcement which has been integrally formed withthe diaphragm, and also integrally formed with respective connectionplates as described later in the method for manufacturing the masssensor of the present invention.

The shape of the plate surface of the diaphragm 31 in the above masssensor 30 is not limited to rectangular as shown in FIG. 5(a), FIG.7(a), and FIG. 9, but various optional shapes, such as circular,triangular, inverted U-shape, polygonal, ellipse, and oval, as shown inmass sensors 30B through 30D of FIGS. 10(a) through (c), may be used.The diaphragm 31 may be not joined to the connection plate 33symmetrically about the Y-axis, as shown in the mass sensor 30E of FIG.10(d). Such an optional selection of the shape of the diaphragm 31 canalso be applied to all the mass sensors of the present invention.

Next, an embodiment of a mass sensor in which only one spring plate isbonded to the mass sensor 30 described above, and is assembled in thesensor substrate is shown in FIG. 11. In the mass sensor 1, it isobviously possible to form the spring plate, spring plate reinforcement,and reinforcing plate described above, or to change the shape of thediaphragm optionally.

FIG. 11 is a plan of a mass sensor 1 viewed from the direction of thediaphragm 3. The mass sensor 1 is designed to be symmetrical. Theoscillation plate 3 constitutes the sensor substrate 2 together with thebase plate 15 and the intermediate plate 17 as described later. Holes 8formed in the sensor substrate 2 are used as alignment marks utilized inpackaging and manufacturing processes of the mass sensor 1, and tworesonating portions 26, one of which is used for referencing, consistingof a diaphragm 19, a connection plate 20, a sensing plate 21, apiezoelectric element 25, and a spring plate 18 as described later areformed. By forming two or more resonating portions 26 in one mass sensor1, including a resonating portion 26 for referencing, signals fromrespective resonating portions 26 can be cumulated to expand the dynamicrange.

The position sensor electrodes 4, 5 are used for sensing the position ofthe mass sensor 1 when the mass sensor 1 is immersed in a conductivespecimen such as an aqueous solution by conducting an electric currentthrough the specimen. When the specimen is conductive, these positionsensor electrodes 4, 5 prevent the second electrode 24 and the firstelectrode 22 on the piezoelectric element 25 (not shown in FIG. 11), andelectrode leads 9, 10 from these electrodes from short-circuiting, bymaking the part above the pattern formed in the horizontal direction ofthe position sensor electrodes 4, 5 immersed in the specimen, and makingthe part of the mass sensor 1 deeper than the position the positionsensor electrodes 4, 5 sensed not immersed in the specimen. To an end ofeach of the position sensor electrodes 4, 5 is formed a terminal 6, 7,respectively; and to an end of each of the electrode leads 9, 10 isformed a terminal 11, 12, respectively. These terminals are connected tothe probes or other connectors on respective sensor instruments.

However, when the piezoelectric element 25 and the electrode leads 9, 10are coated with an insulating resin or the like, since thesepiezoelectric element 25 and electrode leads 9, 10 are notshort-circuited even if the mass sensor 1 is immersed in the conductivespecimen, no position sensors 4, 5, and terminals 6, 7 are required.

FIG. 12 is an enlarged plan showing the sensor portion 13 in FIG. 11viewed from the base plate 15, that is, viewed from the back side of theoscillation plate 3 in FIG. 11. FIG. 13 is a perspective view showingthe vicinity of the cut portion 16 shown in FIG. 12. The sensor portion13 means a portion of the mass sensor 1, comprising the resonatingportion 26 and the sensor substrate 2 in the vicinity of the resonatingportion 26 in the mass sensor 1.

As FIGS. 12 and 13 show, an opening 14 having U-shaped cut portion 16 isformed in the base plate 15. The same shape of cut portion 16 is alsoformed on the intermediate place 17 overlapping the base plate 15, andin the intermediate place 17, an almost prismatic spring plate 18extending toward the center of the opening 14 from the center of thebottom side of the cut portion 16 is formed. However, these intermediateplate 17 and the spring plate 18 are not always required, but are usedas the members constituting the mass sensor 1 when required for theadjustment of the mechanical strength of the resonating portion 26 orthe sensitivity of the mass sensor 1.

In the cut portion 16 of the oscillation plate 3 are formed a connectionplate 20 joined to the spring plate 18, and a diaphragm 19 joined to theupper end of the connection plate 20, but not joined to the spring plate18. Furthermore, in the cut portion 16 of the oscillation plate 3, asensing plate 21 is formed across a side of the connection plate 20 andthe facing side of the cut portion 16.

FIG. 14 shows a perspective view of the vicinity of the cut portion 16shown in FIG. 12 viewed from the oscillation plate 3 side. On thesurface of the oscillation plate 3 side of the sensing plate 21 isformed a piezoelectric element 25 by laminating a first electrode 22, apiezoelectric film 23, and a second electrode 24 in this order.Furthermore, the second electrode 24 is connected to the electrode lead9, and the first electrode 22 is connected to the electrode lead 10.Thus, a sensing portion 29 is constituted of the sensing plate 21 andthe piezoelectric element 25, and the resonating portion 26 isconstituted of the spring plate 18, the diaphragm 19, connection plate20, and the sensing portion 29.

Although only a piezoelectric element 25 is installed on one platesurface of the sensing plate 21 in the mass sensor 1, piezoelectricelements 25 may be installed on both plate surfaces of the sensing plate21. In this case, since the structure of the sensing portion 29 becomessymmetrical, the rigidity of the sensing plates 21 can be equalized.

Also in the mass sensor 1, although a slit 27 is formed on the loweredge of the cut portion 16 in the sensing plate 21 and the oscillationplate 3 as FIG. 13 shows, it is preferable that a structure in which thesensing plate 21 is joined to the lower edge of the cut portion 16 inthe oscillation plate 3 without forming the slit 27, that is, thesensing plate 21 is fitted in and joined to the depression formed by theconnection plate 20 and the sensor substrate 2 as in the mass sensor 42shown in FIG. 15, to restrict the bend of the spring portion consistingof a connection plate 20 and/or a spring plate 18, and to increase thestress applied to the piezoelectric element 25.

In the mass sensor 1 described above, although a sensor portion 13 isinstalled utilizing the circumference of the opening 14 formed in thesensor substrate 2, the sensor portion 13 may be installed on thecircumference of the sensor substrate 2, for example, on the upper edgein FIG. 11. However, since the sheet-like diaphragm 19 is ofteninstalled on the location projected from the cut portion 16, as obviousfrom the structure of the sensor portion 13 shown in FIGS. 11 through14, it is preferable to adopt the structure in which the sensor portion13 is installed inside the sensor substrate 2 as FIG. 11 shows,considering the protection of the resonating portion 26 from externalimpact, for example, so as not to damage the diaphragm 19 on handlingthe mass sensor 1. Such a structure is also preferable for facilitatingthe manufacturing process of the mass sensor 1 as will be describedlater.

Next, various embodiments of mass sensors that can substitute the sensorportion 13 in the mass sensor 1 described above will be described. FIG.16(a) is a plan showing a mass sensor 43A, which is another embodimentof the present invention. The mass sensor 43A has the structure in whicha connection plate 20 and a diaphragm 19 are joined together at therespective sides, two sensing plates 21A, 21B are joined to theconnection plate 20 so as to sandwich the connection plate 20 in thedirection perpendicular to the direction where the diaphragm 19 and theconnection plate 20 are joined, and respective sensing plates 21A, 21Bare also joined to the sensor substrate 2 in the same way as the sensingplate 21 in the mass sensor 42 shown in FIG. 15 and supported and fixedat three sides. This three-side supporting is intended to elevatesensitivity. However, the sensing plates 21A, 21B are not necessarilyrequired to be joined to the lower edge of the depression formed by theconnection plate 20 and the sensor substrate 2.

Piezoelectric elements each consisting of a first electrode, apiezoelectric film, and a second electrode are installed on at least apart of at least one of the plate surfaces of at least one of thesensing plates. In the embodiments shown in FIG. 16, piezoelectricelements 25A through 25D are installed on both plate surfaces of sensingplates 21A, 21B, and the resonating portion is formed of a diaphragm 19,a connection plate 20, the sensing plates 21A, 21B, and thepiezoelectric elements 25A through 25D. However, all the piezoelectricelements 25A through 25D are not necessarily required, but the optionalnumber of the piezoelectric elements may be installed on optionallocations of the sensing plate 21A or 21B.

When a plurality of piezoelectric elements 25A through 25D are used asin this mass sensor 43A, since the rigidity of the sensing plates 21Aand 21B can be equalized, and in addition, the Q values in the θ-modeand the φ-mode can be increased and the Q value of the rotation mode canbe decreased by cumulating or processing signals from the respectivepiezoelectric elements 25A through 25D, resonant frequencies can bemeasured more accurately. Furthermore, when at least two of thepiezoelectric elements 25A through 25D are installed, if one is used fordriving and the other is used for sensing, sensitivity can be improved.Here, it is preferable for improving sensitivity to split thesepiezoelectric elements 25A through 25D in the similar way as thepiezoelectric element 35 is split into piezoelectric elements 35A and35B in the mass sensor 30.

It is also preferable for improving output charge to adopt the structurein which, for example, piezoelectric elements 25A and 25C are installedon the plate surfaces in the same orientation of sensing plates 21A and21B, respectively, and the polarizing direction of the piezoelectricfilms in these piezoelectric elements 25A and 25C is reversed to eachother. It is also preferable to adopt such a structure on respectiveplate surfaces of the sensing plates 21A and 21B. Furthermore, it ispreferable for improving sensitivity to adopt the structure in which atleast one of directions of at least one of the piezoelectric elements25A through 25D, for example, the piezoelectric elements 25C and 25D isa side or two sides of three-side supporting as in the mass sensor 43Bshown in FIG. 16(b). Even in this case, however, it is required that thepiezoelectric elements 25A through 25D do not overlap the spring platewhen the connection plate 20 and the spring plate are used.

When spring plates are bonded to mass sensors 43A, 43B, spring platereinforcements or reinforcing plates can be used as in the mass sensor40B. For example, a reinforcing plate is formed so that it is bonded toa spring plate, and the side of the reinforcing plate is joined to threesides, that is, the sides of the sensor substrate 2 where the sensingplates 21A, 21B, are joined to the sensor substrate 2 (the lateral sideof the cut portion 16), and the side of the sensor substrate 2 where theconnection plate 20 is joined to the sensor substrate 2 (the bottom sideof the cut portion 16). This is preferable for improving sensitivity,because the Q value in the θ-mode can be improved, the resonantfrequency in the flexural mode (the mode bending between the sensorsubstrate and the connection plate) of the piezoelectric element can beincreased, and the frequency in the θ-mode can be increased.

The mass sensor 43C shown in FIG. 16(c) is an embodiment in which a slit48 is formed on the center in the length direction of the connectionplate 20 in the mass sensor 43A. The slit 48 is hollow, and hasfunctions to facilitate oscillation in the θ-mode and the φ-mode of thediaphragm 19 to occur, and the resonant frequency to be identified.Also, as described later, the slit 48 has functions to reduce the massof the connection plate 20 and to improve sensitivity. When a springplate is used, the spring plate may be formed in the shape having such ahollow, and integrated with the connection plate.

When two sensing plates are installed on one resonating portion as shownin FIG. 16(a), the driving force of the diaphragm 19 can be increased byexpanding the area of either one of the sensing plates 21A and 21B bychanging the lengths N₁ and N₂ and the widths M₁ and M₂ of the sensingplates 21A and 21B, and the Q values in the θ-mode and the φ-mode can beincreased by narrowing the area of the other sensing plate, as FIG.17(a) shows. FIG. 17(b) is a sectional view along the X-axis of FIG.17(a) viewed from the Y-axis direction. The Q values in the θ-mode andthe φ-mode can be increased or sensitivity is improved by changing thenatural frequency of the bending displacement oscillation of the sensingplates 21A, 21B determined by the piezoelectric elements 25A, 25B andthe sensing plates 21A, 21B (arrow G in FIG. 17(b)) to f₁ and f₂,respectively, by changing the widths M₁ and M₂ of the sensing plates21A, 21B, for example, by using one of the piezoelectric elements 25A,25B for driving and the other for sensing. Also, the piezoelectricelement having either smaller natural frequencies f₁ and f₂ may be usedfor driving, and the other may be used for failure diagnosing.

When two sensing plates are used in one resonating portion as shown inFIG. 16 or 17, it is also preferable to adopt a structure in which atleast one of the piezoelectric elements 25C, 25D is installed on onesensing plate, for example, the sensing plate 21B, and a slit 28 isformed on the other sensing plate 21A in the direction perpendicular tothe direction where the sensing plate 21A is joined to the connectionplate 20 as FIG. 18 shows. By such a structure, the oscillation in therotation mode can be restricted, the Q values in the θ-mode and theφ-mode can be increased, and the deviation of the resonance point can beincreased to increase the absolute value of the variation of resonantfrequencies. Although the number of the slit 28 may be one, a pluralityof slits are preferable to enhance the effects mentioned above.

Next, FIG. 19(a) shows a plan of a mass sensor 43D, an embodiment inwhich the mass sensor 43A shown in FIG. 16(a) is formed in the opening14 formed in the sensor substrate 2; FIG. 19(b) shows a sectional viewthereof along the broken line A-A in FIG. 19(a). In the mass sensor 43D,two piezoelectric elements 25A, 25C are installed, and electrode leads9, 10 are connected to the piezoelectric elements 25A, 25C,respectively. An insulation coating layer 65 is formed to cover thepiezoelectric elements 25A, 25C and the electrode leads 9, 10. Thisinsulation coating layer 65 protects the piezoelectric elements 25A, 25Cand the electrode leads 9, 10 from short-circuiting even if theresonating portion of the mass sensor 43D is immersed in a conductivespecimen.

The mass sensor 43D is also provided with shield layers 66 comprising aconductive material so as to cover the insulation coating layer 65. Theshield layer 66 are formed on both the surfaces of the sensor substrate2 and connected to each other through a through-hole 67. When sensing anextremely small mass of the 0.1 ng order, it is preferable to alsoshield the wiring members (piezoelectric elements 25A, 25C and electrodeleads 9, 10) on the sensor substrate 2, as well as the wiring from thesensor substrate 2 to the instrument, in order to shield the mass sensorfrom external electromagnetic waves and to minimize the determinationerror of resonant frequencies.

In addition to the aspect of the formation of the shield layer 66 so asto sandwich the sensor substrate 2 as shown in FIG. 19(b), theembodiment in which the shield layer surrounds only the wiring memberson the sensor substrate 2 as shown in the sectional view of FIG. 19(c),and the embodiment in which a shield layer covers only the upper side ofthe wiring members as shown in FIG. 19(d) may also be used.Particularly, the embodiments to shield the entire wiring members asshown in FIGS. 19(b) and (c) are preferable. In the embodiment of FIG.19(a), although the shield layer 66 formed on both the surfaces of thesensor substrate 2 are electrically connected to each other through thethrough-hole 67, these layers may be connected by utilizing the side ofthe sensor substrate 2. The detail of the materials favorably used forthe formation of the insulation coating layer 65 and the shield layer 66will be described later together with the description of materials usedin the mass sensors.

FIG. 20 is a plan view showing another embodiment of a mass sensor ofthe present invention. In the mass sensor 44A shown in FIG. 20(a), aconnection plate 20 is not directly joined to a sensing plate 21, butthe connection plate 20 and the sensing plate 21 are connected to adiaphragm 19 at respective sides so that the directions of joining tothe diaphragm 19 are in parallel to each other, and the diaphragm 19 isnot joined to the sensor substrate 2, but the connection plate 20 andthe sensing plate 21 are connected to the side of the sensor substrate2. That is, the sensing plate 21 also functions as the connection plate20.

A piezoelectric element 25 is installed on at least a part of at leastone of the plate surfaces of the sensing plate 21, and the resonatingportion is formed of the diaphragm 19, the connection plate 20, thesensing plate 21, and the piezoelectric element 25. Whereas, in the masssensor 44B shown in FIG. 20(b), two sensing plates 21A, 21B are formedon both the sides of a connection plate 20, and piezoelectric elements25A, 25B are installed on the sensing plates 21A, 21B, respectively.

Such mass sensors 44A, 44B are suitable for measurement in the θ-mode,because the oscillation of the diaphragm 19 easily occurs in the planeof the diaphragm 19, and the oscillation of the diaphragm 19 in therotation mode is restricted. Since the oscillation of the diaphragm 19is directly transmitted to the piezoelectric element 25 through thesensing plates, the sensitivity of the mass sensors is advantageouslyimproved.

Next, FIGS. 21(a) through (c) are plans showing still another embodimentof the mass sensor of the present invention. First, in the mass sensor45A shown in FIG. 21(a), a diaphragm 72 is joined to two connectionplates 74A, 74B at respective sides so that the connection plates 74A,74B sandwich the diaphragm 72, and the connection plates 74A, 74B bridgeacross the side walls of the depression 76 of the sensor substrate 70 atrespective sides. Here, the depression 76 has a similar function as thecut portion 16 formed in the mass sensor 1, and therefore, may be formedon the side or other portions of the sensor substrate 70 similarly tothe circumference of the sensor substrate 2 shown in FIG. 11 or theopening 14 formed in the sensor substrate 2.

The sensing plates 73A, 73B are provided across the connection plates74A, 74B and the bottom of the depression 76 in the direction whereconnection plates 74A, 74B sandwich the diaphragm 72, that is, in thedirection perpendicular to the Y-axis direction. Furthermore,piezoelectric elements 75A, 75B are installed on at least one of theplate surfaces of the sensing plates 73A, 73B, respectively. Thus aresonating portion is formed of the diaphragm 72, connection plates 74A,74B, sensing plates 73A, 73B, and piezoelectric elements 75A, 75B.

The structure of the mass sensor 45A can be summarized as a mass sensorhaving at least one piezoelectric element, in which a diaphragm 72 issandwiched by and joined to two connection plates at respective sides,the connection plates 74A, 74B bridge across the side walls of theopening or gap formed in the sensor substrate 70, and at least aplurality of sensing plates 73A, 73B are provided across the connectionplates 74A, 74B and the sides of the opening or gap in the directionperpendicular to the direction where the respective connection plates74A, 74B sandwich the diaphragm 72.

In such a mass sensor 45A, the resonant frequency of the resonatingportion on the basis of at least some of, the θ-mode swing oscillationin which the diaphragm 72 performs pendulum-like oscillation on thefixed surface where respective connection plates 74A, 74B are joined tothe sensor substrate 70, centered on the perpendicular axis where thediaphragm 72 perpendicularly passes through the fixed surface, that isthe Y-axis, and in the direction perpendicular to the side of thediaphragm 72 and perpendicular to the Y-axis, that is the X-axis; theφ-mode swing oscillation in which the diaphragm 72 performspendulum-like oscillation centered on the Y-axis in the X-axis directionaccompanying the swing in the direction parallel to the side of thediaphragm 72, that is the Z-axis (not shown); swing oscillation in whichthe diaphragm 72 performs oscillation centered on the Y-axis in theX-axis direction; or rotational oscillation in the plate surface of thediaphragm 72; can be measured by the piezoelectric elements 75A, 75Binstalled on the sensing plates 73A, 73B.

The structures of mass sensors 46A through 46F described later can alsobe summarized similarly to the mass sensors 45A through 45C, and themethod for mass sensing with the mass sensors 46A through 46F is thesame as that of the mass sensors 45A through 45C. However, in the masssensors 46A through 46F, the number of the sensing plates is increasedto four, and in these embodiments, there is added the structure in whichat least a plurality of sensing plates 73A through 73D bridge betweenthe diaphragm 72 and the side of the opening or gap in the directionperpendicular to the direction where respective connection plates 74A,74B sandwich the diaphragm 72.

Therefore, since the diaphragm 72 and the sensing plates 73A, 73B areoscillated in the direction of arrow K in FIG. 21, that is, making theY-axis the center of oscillation, and the direction parallel to theplate surface of the diaphragm 72 and also perpendicular to the Y-axis,that is the X-axis direction, the diaphragm 72 oscillates in thedirection of arrow K stably in the rigid body mode as the θ-mode of thediaphragm 72. There is also an advantage that the flexural mode of thediaphragm 72 is restricted. The shape of the diaphragm 72 is not limitedto rectangular as shown in FIGS. 21(a) through (c), but optional shapesas shown in FIG. 10 can be adopted, and as in the mass sensor 45B shownin FIG. 21(b), the diaphragm 72 may be joined to respective connectionplates 74A, 74B at optional locations. Furthermore, as in the masssensor 45C shown in FIG. 21(c), the respective sensing plates 73A, 73Bmay be supported and fixed at three sides by the respective connectionplates 74A, 74B and the sensor substrate 70 in the same way as thesensing plate 21 in the mass sensor 42 shown in FIG. 15. In the masssensor 45B, a position sensor 77 similar to the position sensors 4,5 ofthe mass sensor 1 is installed.

Next, in mass sensors 46A through 46F, still other embodiments of thepresent invention shown in the plan of FIGS. 22(a) through (f), adiaphragm 72 is sandwiched by and joined to two connection plates 74A,74B at respective sides, the respective connection plates 74A, 74Bbridge across the side walls of the opening 71 of the sensor substrate70, and at least a plurality of sensing plates, here sensing plates 73Athrough 73D, are provided between the respective connection plates 74A,74B and the side wall of the opening 71, or between the diaphragm 72 andthe side wall of the opening 71 in the direction perpendicular to thedirection where the connection plates 74A, 74B sandwich the diaphragm72.

Furthermore, piezoelectric elements 75A through 75D are installed on atleast one of the plate surfaces of at least one of the sensing plates73A through 73D, and thus a resonating portion is formed of a diaphragm72, connection plates 74A, 74B, sensing plates 73A through 73D, andpiezoelectric elements 75A through 75D.

When mass sensors 46A through 46F shown in FIGS. 22(a) through (f) areseen, in the mass sensor 46A shown in FIG. 22(a), rotation of thediaphragm 72 about the Y-axis is restricted by the sensing plates 73A,73B compared with the structures of mass sensors 45A through 45C shownin FIG. 21. It is preferable to form slits 28 on the sensing plates 73A,73B as in the embodiment shown in FIG. 17 because the diaphragm 72oscillates easily in the direction of arrow K.

In the mass sensor 46B of FIG. 22(b), piezoelectric elements 75A through75D are installed on the surfaces of all of the sensing plates 73Athrough 73D shown in FIG. 22(a) oriented to the same direction. By this,the amplitude of the diaphragm 72 oscillating in the K direction isincreased, and the mass sensor can be suitably used for the measurementin high viscous substances as well as in low viscous substances. At thistime, the direction of the polarization of piezoelectric films of thepiezoelectric elements 75A and 75C, and 75B and 75D should be oppositeto each other. Furthermore, the piezoelectric elements 75A through 75Dmay be installed on both sides of the sensing plates 73A through 73D.

FIG. 22(c) shows a mass sensor 46C in which a side of sensing plates 73Athrough 73D in the embodiments shown in FIGS. 22(a) and (b) facing tothe sensor substrate 70 is joined to the sensor substrate 70. By such astructure, the effects obtained by the structure of the mass sensor 42shown in FIG. 15 can be added to the effects of the embodiments shown inFIGS. 22(a) and (b).

In the mass sensor 46D of FIG. 22(d), piezoelectric elements 75B, 75Care installed on the sensing plates 73B, 73C located point-symmetricallyabout the intersection of the X-axis and the Y-axis, which is the centerof the diaphragm 72. Since the resonant frequency is sensed using therigid body mode in which oscillation in the η direction around theintersection of the X-axis and the Y-axis (direction of the arrow inFIG. 22(d)) is dominant, the sensing plates 73A, 73D are not necessarilyrequired. When the sensing plates 73A, 73D are formed, slits orpiezoelectric elements 75A, 75D may be provided on the sensing plates73A, 73D. In this case, it is preferable that the directions ofpolarization of respective piezoelectric films in each set of thepiezoelectric elements 75A and 75D, and 75B and 75C are the same.

In the mass sensor 46E of FIG. 22(e), sensing plates 73A through 73D arejoined to the diaphragm 72, and the locations of the piezoelectricelements 75A through 75D are the same as in the case of FIG. 22(b). Theoscillation of the diaphragm 72 in the direction of arrow K can also besensed by such a structure. Furthermore, the mass sensor 46F shown inFIG. 22(f) has the structure which oscillates easily in the θ-mode andthe φ-mode by increasing the width of either one of the connectionplates 74A, 74B, and decreasing the width of the other.

Thus, although various shapes can be selected in the mass sensors of thepresent invention, materials used for producing these mass sensors arenot changed depending on respective mass sensors. Then, membersconstituting a mass sensor of the present invention and their shapeswill be described using the mass sensor 1 described above. First, thesensor substrate 2, diaphragm 19, connection plate 20, sensing plate 21,and spring plate 18 are preferably made of ceramics, for example,stabilized or partially stabilized zirconia, alumina, magnesia, orsilicon nitride. Among these, stabilized or partially stabilizedzirconia is most preferably used because they have a high mechanicalstrength even in case of a thin plate, a high toughness, and a lowreactivity with the materials of piezoelectric films or electrodes.

When stabilized or partially stabilized zirconia mentioned above is usedas the material for the sensor substrate 2, it is preferable to add anadditive such as alumina and titania at least to the sensing plate.

Although the oscillation plate 3, intermediate plate 17, and base plate15 in the sensor substrate 2, and the diaphragm 19, connection plate 20,spring plate 18, and sensing plate 21 are not necessarily required to becomposed of the same material, and various ceramic materials may be usedin combination depending on the design, it is preferable to constitutethese members integrally using the same material from the point of viewof the reliability of the parts where these members are joined, and thesimplification of the manufacturing process.

However, when the spring plates 18 are formed on both the plate surfacesof a connection plate 20, the spring plate formed on the surface onwhich a piezoelectric element 25 is installed can be produced to havethe same structure as the piezoelectric element 25. This is preferablefor the manufacturing process, since the spring plate can be formedsimultaneously with the piezoelectric element 25. However, for thepiezoelectric element formed as a spring plate, the electrode is notused as the electrode.

Although a major purpose of the mass sensor 1 is sensing a mass of the0.1 nanogram (ng) order, the thickness of the diaphragm 19 is preferablyabout 3 to 20 μm, more preferably about 5 to 15 μm, and the thickness ofthe base plate 15 is suitably determined considering the ease ofoperation.

When a spring plate 18 is formed, in either case where it is bonded onone side or on both sides of the connection plate 20, the thickness ispreferably 10 to 220 μm, the width is preferably 100 to 500 μm, and theaspect ratio (width/thickness) of the spring plate 18 is preferably in arange between 0.4 and 50. When the attenuation of oscillation amplitudeby the use of the mass sensor 1 in a liquid is considered, the thicknessis preferably 10 to 70 μm, the width is preferably 100 to 500 μm, andthe aspect ratio is preferably 1.4 to 50. More preferably, the thicknessis 10 to 70 μm, the width is 100 to 300 μm, and the aspect ratio is 1.4to 30. The thickness of the spring plate reinforcement, when such aspring plate reinforcement is required, is preferably the same as thethickness of the spring plate being joined to the spring platereinforcement.

Whereas, the connection plate 20 may be used as a spring plate withoutforming the spring plate 18. In this case, no intermediate plate 17 maybe formed, but it is preferable to increase the thickness of the baseplate 15 by the thickness of the intermediate plate 17 for maintainingthe mechanical strength of the sensor substrate 2.

For the piezoelectric film 23 in the piezoelectric element 25, althoughfilm-like piezoelectric ceramics are suitably used, electrostrictionceramics or ferroelectric ceramics may also be used. Such materials maybe either those requiring or not requiring polarization.

Ceramics that can be used in the piezoelectric film 23 include, forexample, lead zirconate, lead titanate, lead magnesium niobate, leadnickel niobate, lead zinc niobate, lead manganese niobate, lead antimonystannate, lead manganese tungstate, lead cobalt niobate, and bariumtitanate. These may be used alone, or as ceramics containing thecombination of some of them. In the present invention, a materialcontaining the components consisting mainly of lead zirconate, leadtitanate, and lead magnesium niobate as the main component is preferablyused, because such a material not only has high electrical-mechanicalcoupling coefficient and piezoelectric constant, but also has smallreactivity with the sensor substrate member on sintering piezoelectricfilm, and can form the desired composition stably.

Furthermore, ceramics containing the oxides of lanthanum, calcium,strontium, molybdenum, tungsten, barium, niobium, zinc, nickel,manganese, cerium, cadmium, chromium, cobalt, antimony, iron, yttrium,tantalum, lithium, bismuth, and tin alone, or in the combination of someof these oxides, or ceramics in which other compounds of these elementsare added may be used for the above piezoelectric ceramics. For example,a ceramic material containing lead zirconate, lead titanate, and leadmagnesium niobate as main components, to which lanthanum or strontium isadded is also preferable, and such a material to which manganese isfurther added is preferable because the mechanical quality factor islarge, and the Q value can be increased not only from the structure ofthe sensor but also from the material.

On the other hand, the first electrode 22 and the second electrode 24 inthe piezoelectric element 25 are preferably formed from a metal that issolid at room temperature and conductive. For example, a metal such asaluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc,niobium, molybdenum, ruthenium, palladium, rhodium, silver, tin,tantalum, tungsten, iridium, platinum, gold, or lead alone, or an alloyof some of these elements can be used. Furthermore, a cermet material inwhich the same material used in the piezoelectric film 23 or the sensingplate 21 is dispersed in these materials may be used.

The selection of the material for the actual first electrode 22 and thesecond electrode 24 is determined depending on the method for formingthe piezoelectric film 23. For example, when the first electrode 22 isformed on the sensing plate 21, then the piezoelectric film 23 is formedon the first electrode 22 by sintering, the first electrode 22 must bemade of a high melting point metal, such as platinum, which is notaffected by the temperature for sintering the piezoelectric film 23.However, since the second electrode formed on the piezoelectric film 23after forming the piezoelectric film 23 can be formed at a lowtemperature, a low melting point metal, such as aluminum, can be used.

Although the piezoelectric element 25 can be formed integrally bysintering, in this case, both the first electrode 22 and the secondelectrode 24 must be made of a high melting point metal which resiststhe temperature for sintering the piezoelectric film 23. On the otherhand, when the first and second electrodes 59, 60 are formed on thepiezoelectric film 58 after forming the piezoelectric film 58, as in thepiezoelectric element 62A shown in FIG. 3, both electrodes can be madeof the same low melting point metal, but when the piezoelectric element62A is simultaneously sintered, both the first electrode 22 and thesecond electrode 24 must be made of a high melting point metal. Thus,the materials for the first electrode 22 and the second electrode 24 canbe selected suitably depending on the temperature for forming thepiezoelectric film 23 represented by the sintering temperature of thepiezoelectric film 23, and the structure of the piezoelectric element25. The materials and methods for forming the electrode leads 9, 10 arethe same as those for the first electrode 22 and the second electrode 24of the piezoelectric element 25.

Since a problem arises when the area of the piezoelectric film 23 isexpanded, in that although sensitivity increases because of increase inthe output charge, the size of the sensor increases, the area of thepiezoelectric film 23 should be designed to an adequate size. Also,since a problem arises when the thickness of the piezoelectric film 23is decreased, in that although sensitivity increases, the rigidity ofthe piezoelectric film 23 is lowered, the total thickness of the sensingplate 21 and the piezoelectric film 23 is preferably 15 to 50 μm.

When an insulation coating layer 65 is formed on the piezoelectricelement 25 and the electrode leads 9, 10 as in the mass sensor 43D shownin FIG. 19, insulating glass or resin is used as its material. Forenhancing the performance of the mass sensor 1, a resin is morepreferably used as the material for the insulation coating layer thanglass, and chemically stable fluorine resins, for example,tetrafluoroethylene-based Teflon (Teflon PTFE of DuPont),tetrafluoroethylene-hexafluoropropylene copolymer-based Teflon (TeflonFEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer-basedTeflon (Teflon PFA), and PTFE/PFA composite Teflon are preferably used.Although corrosion resistance and weather resistance are lower thanthose of these fluorine resins, silicone resins (in particular,thermosetting silicone resins) can be suitably used, and epoxy resins oracrylate resins can also be used depending on the applications. It isalso preferable to form the insulation coating layer 65 using differentmaterials for the piezoelectric element 25 and its vicinity, and theelectrode leads 9, 10 and their vicinity. Furthermore, it is alsopreferable to add inorganic or organic fillers in the insulating resinto adjust the rigidity of the resonating portion.

When the insulation coating layer 65 is formed, the materials for ashield layer 66 formed on the insulation coating layer 65 are preferablymetals such as gold, silver, copper, nickel, and aluminum; however, anymetallic materials used in the first electrode 22 of the piezoelectricelement 25 or the like described above can be used. A conductive pastecomprising metal powder mixed in a resin may also be used.

Next, the method for using a mass sensor of the present invention willbe described when the mass sensor 1 is used as an immune sensor. One oftwo sensor portions 13 is used as a detection sensor portion 13D. To thediaphragm of the detection sensor portion 13D is applied a catchingsubstance which reacts with only a substance to be sensed, such as apathogenic virus, and catches it. For example, the combination of anantigen as the substance to be sensed, and an antibody as the catchingsubstance can be used. The examples of such combinations include humanserum albumin/anti-human serum albumin antibody and humanimmunoglobulin/anti-human immunoglobulin antibody. Whereas, the othersensor portion 13 is used as a reference sensor portion 13R, to thediaphragm of which no catching substance is applied.

Both sensor portions 13D and 13R are immersed in or placed on the samespecimen. In many cases, since specimens are fluids such as liquids orgases, the specimens can be tested by comparing the signals from thesensor portions 13D and 13R, without being influenced by the physicalproperties of the specimens such as type and, flow, and temperature ofthe fluid, or the testing environment.

When this mass sensor 1 is immersed in, for example, a conductive liquidspecimen, if the mass sensor 1 is immersed in the specimen to the levelwhere the position sensor electrodes 4, 5 are short-circuited, thediaphragms 19 of the sensor portions 13D and 13R are immersed in thespecimen, but the sensing portion 29 is not short-circuited by thespecimen. However, when the piezoelectric element 25 and the electrodeleads 9, 10 are coated by insulating glass or resin, the areas of themass sensor 1 other than terminals 11, 12, or other connectors, can beimmersed in the specimen.

Thus, when the substance to be sensed in the specimen reacts with and iscaught by the catching substance, the mass of the diaphragm 19 in thedetection sensor portion 13D increases, and the resonant frequency ofthe resonating portion 26 varies accompanying this increase in the massof the diaphragm 19. Therefore, on the contrary, by observing change inthe resonant frequency of the resonating portion 26, whether or not thesubstance to be sensed has been caught on the diaphragm 19, that is,whether or not the substance to be sensed was present in the specimen,can be determined, and increase in the mass can be measured.

In the method for using the two sensor portions 13 as a detection sensorportion 13D and a reference sensor portion 13R, if the resonatingportion in the reference sensor portion 13R, that is, the diaphragm,connection plate, sensing plate, piezoelectric element, and spring plateare coated by Teflon, the adhesion of the substance to be sensed to thereference sensor portion 13R can be prevented, and more accuratemeasurement can be performed. If the detection sensor portion 13D otherthan the diaphragm 19 is similarly coated by Teflon, the substance to besensed can be caught only on the diaphragm 19, and sensitivity iselevated. Furthermore, it is economically preferable to coat the entiresensor substrate 2 other than the diaphragm 19 with Teflon in order toapply an expensive catching substance such as an antibody only to arequired location.

When the mass sensor 1 is immersed in a specimen, such as a liquid, or adiaphragm 19 is dipped in a catching substance for applying the catchingsubstance to the diaphragm 19, the structure is adopted in which twosensor portions 13 are arranged in the lateral direction of the sensorsubstrate 2 (horizontal direction) in FIG. 11, so that the two sensorportions 13 are simultaneously immersed in the specimen.

However, if the two sensor portions 13 are arranged in the perpendiculardirection of the sensor substrate 2 (up-down direction), that is, on theposition where the detection sensor portion 13D is first immersed in theliquid, and the reference sensor portion 13R is not immersed in theliquid, the process can easily be performed, in which only the area ofthe detection sensor portion 13D is immersed in the catching substancefor applying, and the reference sensor portion 13R is used as a sensorsuch as a temperature compensating sensor without teflon coating, and isnot immersed in the catching substance, that is not to apply thecatching substance.

However, even in using the mass sensor 1 in which the catching substanceis applied only to the detection sensor portion 13D, the detectionsensor portion 13D and the reference sensor portion 13R must be placedin the same environment on actual mass sensing. Also, when the entiremass sensor 1 is immersed in a conductive liquid, the piezoelectricelements 25 and the electrode leads 9, 10 in the sensor portions 13R,13D must obviously undergo insulation coating.

The using method, in which the same catching substance is applied to thediaphragms of both sensor portions 13D and 13R to expand the dynamicrange by adding the signals from the sensor portions 13D and 13R, isalso possible. Furthermore, it is also possible not to use the referencesensor portion 13R for referencing, and a catching substance differentfrom that applied to the detection sensor portion 13D is applied to thereference sensor portion 13R.

On the measurement of change in the resonant frequency in the masssensor 1 with these using methods, it is preferable to sense theresonant frequencies in the θ-mode and the φ-mode as described above.For example, as FIG. 14 shows, when the diaphragm 19 generates swingoscillation in the θ-mode about the spring plate 18 and the connectionplate 20 in the plate surface of the diaphragm 19, the movement istransmitted to the sensing plate 21 to cause the bending oscillation ofthe sensing plate 21 and the stretching oscillation of the planerpiezoelectric film 23 in the piezoelectric element 25 on the surface ofthe sensing plate 21, and a constant voltage is generated on the basisof the electrical-mechanical coupling coefficient k₃₁ (piezoelectricfactor d₃₁) of the piezoelectric film 23. When the piezoelectric element25 has a comb-shaped electrode structure, a constant voltage isgenerated on the basis of k₃₃ (d₃₃). This is the same when the φ-mode isused.

On the contrary, when an alternating current is applied to thepiezoelectric film 23 through the second electrode 24 and the firstelectrode 22, stretching oscillation is generated in the piezoelectricfilm 23 by d₃₁ or d₃₃ causing the sensing plate 21 to generate bendingoscillation, and the oscillating angle θ of the diaphragm 19 variescorresponding to the mass of the diaphragm 19, and resonant oscillationis generated at a certain frequency. Therefore, the observation ofchange in the resonant frequency is the observation of change in themass of the diaphragm 19, and whether or not a substance to be sensed iscaught on the diaphragm 19 can be determined. By installing twopiezoelectric elements 25 on both plate surfaces of the sensing plate 21and comparing obtained signals, noise can be reduced, the effect ofother oscillation modes can be eliminated, and sensitivity can beimproved.

Here, in order to further improve the sensitivity of the mass sensor 1,change in the resonant frequency of the resonating portion 26 must beincreased. As a means for this, a method for controlling the ratio ofmasses of the diaphragm 19 and the spring plate 18 can be used. As thespring plate 18 is thinned to reduce the mass, and the mass ratio withthe diaphragm 19 (mass of the diaphragm 19/mass of the spring plate 18)is increased, sensitivity is improved.

However, since the rigidity of the spring plate 18 is lowered withdecrease in the thickness and the mass of the spring plate 18, the massratio (mass of the diaphragm 19/(mass of the spring plate 18+mass of theconnection plate 20)) is preferably 0.1 or more within a range where therigidity of the spring plate 18 and the connection plate 20 is secured,considering the thickness and area of the diaphragm 19, but it ispreferable to determine the suitable ratio considering the area of thediaphragm 19. However, these mass ratios are preferably determinedwithin the range where the conditions of the thickness, width, and theaspect ratio of the spring plate 18 described above are satisfied. Themass sensor 43C shown in FIG. 16(c) is one of the examples.

As another means for improving sensitivity, a method to decrease thethickness of the diaphragm 19 for increasing the mass ratio with asubstance to be sensed (mass of the substance to be sensed/mass of thediaphragm 19), that is, the proportion of change in the mass of thediaphragm 19 can be used. Furthermore, when the thickness of thediaphragm 19 is decreased, if the surface area of the diaphragm 19 isincreased without decreasing the mass, the area to which the catchingsubstance is applied can be increased, and more substance to be sensedcan be caught, resulting in the improvement of sensitivity.

Next, other applications of the mass sensor 1 will be described. First,when the catching substance applied to the diaphragm 19 is a moistureadsorbing material, the mass sensor 1 can be used as a moisture meter.When applying to the diaphragm 19 an adsorbing material that adsorbs aspecific gaseous component, or an organic or inorganic substance as acatching substance, the mass sensor 1 can be used as a gas sensor, anodor sensor, or a taste sensor. Furthermore, if the temperature of thediaphragm 19 is controlled to make moisture condense, the mass sensor 1can be used as a dew point meter which measures the dew point from thetemperature when the mass of the diaphragm 19 is increased.

The mass sensor 1 can also be used as a film thickness meter. The filmsthat can be measured include sputtered films or CVD films formed invacuum, LB films formed in gases, or electrodeposited films formed inliquids. When these films are formed, if the diaphragm 19 or theresonating portion 26 of the mass sensor 1 is placed in the same filmforming environment, a film is formed on the diaphragm 19 or theresonating portion 26 causing change in the mass, and change in resonantfrequency, the thickness or the growing speed of the formed film can bemeasured.

Although a quartz vapor deposited film thickness meter has been known todetect change in the resonant frequency of a quartz oscillator 80similar to the one shown in FIG. 27 in the slipping direction when thefilm thickness changes, it has problems in that it is affected by changein temperature, noise due to the collision of impurities, and change invacuum pressure, because the oscillator itself is used in a vapordeposition environment.

Whereas, if the mass sensor 1 is used in the θ-mode as a vapor depositedfilm thickness meter, the sensing portion 29 resists change intemperature because of the rigid body mode, the probability of thecollision of impurities is low because the diaphragm 19 is as thin as 3to 20 μm, and a structure in which the sensing portion 29, spring plate18, and the connection plate 20 are easily held in a constantenvironment, the measurement accuracy can be improved compared with thecase where a quartz oscillator 80 is used.

Furthermore, the mass sensor 1 can be used as a viscosity meter to causethe shear waves of transverse waves to occur in a fluid when thediaphragm 19 is immersed in the liquid, and receive the mass load of theportion where viscous waves enter.

Although a quartz viscosity meter for detecting change in the resonantfrequency of a quartz oscillator 80 in the slipping direction is alsoused, it has problems in that it is affected by change in temperature,and noise due to the collision of impurities in the liquid, because thequartz oscillator 80 itself is immersed in the liquid.

On the other hand, when the mass sensor 1 is used in the θ-mode as aviscosity meter, since the sensing portion 29, the spring plate 18, andthe connection plate 20 are not required to be immersed in the liquid,the sensing portion 29 resists change in temperature because of therigid body mode, and the diaphragm 19 is as thin as 3 to 20 μm, theprobability of the collision of impurities is low, sensitivity isimproved.

Furthermore, a quartz oscillator is used as a friction vacuum metersince its electric resistance varies due to the friction of gasmolecules and the viscous friction of the gas in a vacuum. However,since this type of vacuum meter is used to measure change in frequenciesdue to the mass load effect of the quartz oscillator, the mass sensor 1of the present invention utilizing basically the same measurementprinciple can also be used as a vacuum meter.

Although a friction vacuum meter using a quartz oscillator detectschange in resistance when the tuning fork-shaped oscillator 90 isoscillated in the X-axis direction as FIG. 28 shows, it is difficult todecrease the thickness d₁ of the oscillator 90, and therefore, theimprovement of sensitivity is difficult. Whereas, in the mass sensor 1,the thickness of the diaphragm 19 can be decreased to 3 to 20 μm, andthe θ-mode can be used, sensitivity can be improved.

In addition, the mass sensor 1 can be used as a temperature sensor byusing the bending mode of the diaphragm 19, that is, by sensing changein the Young's modulus as change in resonant frequency in the bendingmode.

Although the mass sensor 1 can be used as various sensors, the basicprinciple of measurement is to measure change in the resonant frequencyof the resonating portion 26 on the basis of the mass load to thediaphragm 19. Therefore, a plurality of sensor portions 13 havingdifferent functions can be formed easily in one mass sensor 1. Forexample, the functions of a temperature sensor, a vacuum meter, or aviscosity sensor can be added to the function as the mass sensor 1, thatis, a sensor for referencing for the compensation of temperature,vacuum, or viscosity can be easily incorporated in the mass sensor 1. Insuch cases, since it is not necessary to use a plurality of sensorshaving different shapes for different applications, it is alsoadvantageous from the costs for the incorporation of sensors to theplace of measurement and their handling, and for the measuringinstruments.

Next, a method for fabricating a mass sensor of the present inventionwill be described using the mass sensor 1 as an example. As thematerials of the sensor substrate, ceramics such as zirconia aresuitably used. A slurry is produced by mixing a binder, solvent,dispersing agent, and other additives in ceramic powder, and afterremoving foams from the slurry, a green sheet or a green tape for theoscillation plate, intermediate plates and base plates having desiredthickness using a method such as the reverse roll coater method and thedoctor blade method is formed.

Next, these green sheets are punched using a die or laser to desiredshapes, for example, as shown in FIG. 23, the shape of an intermediateplate 17 having an opening 14 and a spring plate 18, and the shape of abase plate 15 having an opening 14, and the green sheet at least one foreach of the oscillation plate, the intermediate plate 17, and the baseplate 15 are laminated in this order, and sintered and integrated toform the sensor substrate. On laminating these green sheets, holes 8 areformed in each green sheet for the alignment of lamination. The shapesof the green sheets shown in FIG. 23 are simplified for easyunderstanding of the formation of the sensor portion 13 of the masssensor 1 shown in FIG. 11.

Although an opening 14 or a diaphragm 19 can be also formed in theoscillation plate 3 in green state, since the oscillation plate is asthin as 20 μm or lesser, it is preferable to form the opening 14 or thediaphragm 19 in a predetermined shape after forming the sensor substrate2 and installing the piezoelectric element 25 by laser processingdescribed later, for securing the flatness and dimensional accuracyafter sintering of the diaphragm 19, connection plate 20, and sensingplate 21 formed in the oscillation plate 3.

Methods for installing the piezoelectric element 25 consisting of afirst electrode 22, a piezoelectric film 23, and a second electrode 24on the area of the oscillation plate 3 where the sensing plate 21 isformed include a method in which a piezoelectric film 23 is formed bypress formation using a die or tape formation using a slurry material,the piezoelectric film 23 before sintering is overlaid by heat andpressure on the area of the oscillation plate 3 where the sensing plate21 is formed, and they are simultaneously sintered to form the sensorsubstrate 2 and the piezoelectric film 23 at the same time. In thiscase, however, the electrodes 22, 24 must be formed on the sensorsubstrate 2 or the piezoelectric film 23 beforehand by the filmformation method described later.

Although the temperature for sintering the piezoelectric film 23 isdetermined depending on the constituting material, it is generally 800°C. to 1400° C., preferably 1000° C. to 1400° C. In this case, it ispreferable for controlling the composition of the piezoelectric film 23,that sintering is conducted in the presence of the evaporation source ofthe material for the piezoelectric film 23. When the sintering of thepiezoelectric film 23 and the sintering of the sensor substrate 2 areperformed simultaneously, the sintering conditions of the two must bematched to each other.

On the other hand, if the film formation method is used, thepiezoelectric element 25 can be installed on the area of the sinteredsensor substrate 2 where the sensing plate 21 is formed, by variousthick film forming methods, such as screen printing, dipping, andpainting; or various thin film forming methods, such as the ion beammethod, sputtering, vacuum deposition, ion plating, chemical vapordeposition (CVD), or electroplating. Among these, for the formation ofthe piezoelectric film 23 in the present invention, thick film formingmethods, such as screen printing, dipping, and painting are preferablyused. This is because the piezoelectric film 23 can be formed usingpaste or slurry consisting mainly of the particles of piezoelectricceramics having an average particle diameter of 0.01 to 5 μm, preferably0.05 to 3 μm, and favorable piezoelectric properties are obtained.

For example, after the sensor substrate 2 has been sintered underpredetermined conditions, the first electrode 22 is printed and sinteredon the predetermined surface area of the oscillation plate 3, then thepiezoelectric film 23 is printed and sintered, and further, the secondelectrode 24 is printed and sintered to form the piezoelectric element25. Then, electrode leads 9, 10 are printed and sintered for connectingthe electrodes 22, 24 to the measurement apparatus. Here, for example,if platinum (Pt) is used for the first electrode 22, lead zirconatetitanate (PZT) is used for the piezoelectric film 23, gold (Au) is usedfor the second electrode 24, and silver (Ag) is used for the electrodeleads 9, 10, sintering temperatures in the sintering process can belowered stepwise. Therefore, the previously sintered materials are notsintered again in a certain sintering step, and the occurrence oftroubles in the material for electrodes or the like, such as peeling offand aggregation, can be avoided.

By selecting suitable materials, the respective members of thepiezoelectric element 25 and electrodes 9, 10 can be printed one afterthe other, and integrally sintered at once, or after the piezoelectricfilm 23 is formed, respective electrodes or the like can be formed at alow temperature. Also, the respective members of the piezoelectricelement 25 and electrodes 9, 10 can be formed by a thin film formingmethod, such as sputtering or vapor deposition. In this case, heattreatment is not necessarily required.

Thus, it is particularly preferable to form the piezoelectric element 25using the film formation method, since the piezoelectric element 25 andthe sensing plate 21 can be integrally joined and installed withoutusing adhesives, and the mass sensor excels in reliability andreproducibility, and is easily integrated. Here, the piezoelectric film23 may be suitably patterned, and the methods for patterning include,for example, screen printing, photolithography, laser processing, ormechanical processing such as slicing and ultrasonic processing.

Next, a diaphragm 19 is formed on the predetermined area of thus formedsensor substrate. Here, it is preferable to remove the unnecessary partof the oscillation plate 3 by processing using the fourth harmonic ofYAG laser. Thus, for example, an opening 14 can be formed leavingmembers integrally joined to the sensor substrate 2, such as thediaphragm 19 and the sensing plate 21 as shown in FIG. 11 or 12, and atthis time, by adjusting the shape of the diaphragm 19 or the like, theresonant frequency can be adjusted to the predetermined value, and therange of masses of the substance to be sensed can be determined.

Here, as shown in FIG. 24 if a part of the diaphragm 19 is cut andremoved so that the length of the diaphragm 19 is decreased from L₀ toL₁, the resonance point can be raised, and on the other hand, if thewidth of the spring plate 18 and the connection plate 20 is narrowedfrom t₀ to t₁, the resonance point can be lowered. Therefore, by thecombination of these values, the resonance point can be adjusted.Furthermore, by narrowing the width of the diaphragm 19 from W₀ to W₁,the rotation mode can be restricted, the Q value in the θ-mode can beincreased, and the difference of change in the resonant frequenciesdepending on an adhesion location can be decreased even when the mass ofthe adhered substance is the same.

Furthermore, as FIG. 25 shows, after a piezoelectric element 25comprising a first electrode 22 as the upper electrode, a secondelectrode 24 as the lower electrode, and a piezoelectric film 23 formedtherebetween is once formed, the upper electrode can be removed by thefourth harmonic of YAG laser, or machining to adjust the effectiveelectrode area of the piezoelectric element and adjust sensitivity. Whenthe structure of the piezoelectric element 25 is a comb structure asshown in FIG. 3 or 4, part of one or both electrodes may be removed.

In processing such a resonating portion, various processing methodssuitable for the size and shape of the resonating portion, such as laserprocessing with YAG laser, the second or third harmonic of YAG laser,excimer laser, or CO₂ laser; electron beam processing; and dicing(machining), in addition to the fourth harmonic of YAG laser describedabove.

In addition to the method using green sheets as described above, thesensor substrate 2 can be produced by the compression molding usingmolds, slip casting, or injection molding. In these cases also,machining such as cutting, grinding, laser processing, press punching,and ultrasonic processing is conducted before and after sintering, andthe mass sensor 1 of a predetermined shape is obtained.

When an insulation coating layer 65 is formed on the piezoelectricelement 25 and electrode leads 9, 10 in thus fabricated mass sensor 1,as in the mass sensor 43D shown in FIG. 19, it can be formed using glassor a resin by screen printing, painting, or spraying. Here, when glassis used as the material, the mass sensor 1 itself must be heated to thesoftening point of the glass, and since glass has a high hardness,oscillation may be inhibited. However, since the resin is soft, and onlysuch processing as drying is required, the use of a resin is preferable.Although it has already been described that fluorine or silicone resinsare suitable as resins that can be used in the insulation coating layer65, it is preferable, when these resins are used, to form a primer layersuited to the types of the resin and ceramics used, for improving theadhesion with the underlying ceramics, and to form the insulationcoating layer 65 on the primer layer.

Next, when a shield layer 66 formed on the insulation coating layer 65is made of a resin, since sintering is difficult, a method not requiringheat, such as sputtering, is used when various metallic materials areused as conductive members; however, when a conductive paste comprisingmetal powder and a resin is used, screen printing or painting can beused preferably. If the insulation coating layer 65 is made of glass, apaste containing a metal can be screen-printed, and sintered below atemperature at which the glass flows.

Finally, a catching substance or the like is applied to the entirediaphragm 19 or resonating portion 26 to complete the mass sensor 1. Themeasurement of resonant frequencies is performed using an impedanceanalyzer or a network analyzer, or by the SINSWEEP system, or throughthe measurement of transfer functions by oscillating by externalultrasonic waves. Furthermore, change in the mass of the diaphragm 19can be measured from change in the resonant frequencies.

The present invention will be described below referring to the example;however, this example is not intended to limit the present invention.

In the fabrication of the mass sensor having the structure shown in FIG.11, green sheets having different thicknesses were prepared for theoscillation plate, the intermediate plate, and the base plate fromzirconia which had been partially stabilized by yttrium oxide, processedin predetermined shapes, laminated in this order, heated and compressed,and integrally sintered at 1450° C. Next, a piezoelectric elementconsisting of a first electrode, a piezoelectric film, and a secondelectrode, and electrode leads connected to these electrodes were formedon the predetermined area of the oscillation plate on which the sensingplate was formed by the screen-print method. The first electrode wasmade of platinum; the piezoelectric film was made of a materialcontaining lead zirconate, lead titanate, and lead magnesium niobate asmain components; the second electrode was made of gold; and theelectrode leads were made of silver.

Next, YAG laser processing (fourth harmonic, wavelength: 266 nm) wasperformed so that an opening, a diaphragm, and a sensing plate wereformed in the sensor portion 13 shown in FIG. 12 to complete the masssensor 1. Here, the thickness of the diaphragm was 7 μm, the thicknessof the intermediate plate was 65 μm, the thickness of the base plate was150 μm, and the dimension of the diaphragm was 0.5 mm×0.3 mm.

The mass on the diaphragm was changed by forming a plurality of spotpatterns of 10 μmφ in diameter in a gold layer of a thickness of 0.3 μmformed on an entire surface of the diaphragm with YAG laser as describedabove to decrease the mass. The resonant frequencies before and afterprocessing were observed, and the results shown in FIG. 26 wereobtained. From these results, it was verified that the mass sensor ofthe present invention exhibited change in resonant frequenciescorresponding to change in the mass of a nanometer order.

The mass sensor of the present invention has been described focussing apiezoelectric conversion device using a piezoelectric film that utilizesthe piezoelectric effect as a device for sensing the oscillation of aresonating portion and inverting the oscillation to electric signals.However, such oscillation signal converting devices are not limited tothose utilizing the piezoelectric effect, but may be constituted bythose utilizing electromagnetic induction, change in electrostaticcapacity, change in incident light, change in electric resistance, orpyroelectricity.

For example, those utilizing electromagnetic induction include thosehaving a coil installed on the sensing plate, an electric circuit fordetecting electric signals flowing in the coil, and a magnet (may be anelectromagnet) for generating a magnetic field in the coil. In thiscase, when the coil oscillates together with the resonating portion, anelectric current flows through the coil due to electromagneticinduction, and the electric current is detected by the electric circuit.Those utilizing change in electrostatic capacity include those having apair of electrodes installed on the surface of the sensing plate, adielectric sandwiched by these electrodes, and an electric circuitconnected to these electrodes, and detecting the electrostatic capacitycharged in this specific space with the electric circuit.

Those utilizing change in incident light include those having a devicefor illuminating the resonating portion such as a photodiode, and adevice for measuring the quantity of light reflected by the resonatingportion (light receiver). This light receiver may be a photo sensor. Asthe resonating portion oscillates, the quantity of light reflected bythe resonating portion changes, and change in the quantity of theincident light is measured by the light receiver.

Those utilizing change in electric resistance are roughly divided intothat using a conductor and that using a semiconductor. That using aconductor has a conductor provided on the surface of the resonatingportion, and an electric circuit connected to the conductor. Since theconductor is distorted by oscillation when the conductor oscillatestogether with the resonating portion and its resistance changes, thischange in resistance is detected by the electric circuit. That using asemiconductor uses a semiconductor in place of the conductor.

Those utilizing pyroelectricity include those comprising a pair ofelectrodes provided on the surface of the sensing plate, a pyroelectricmember formed between these electrodes, an electronic circuit connectedto the electrodes, and a heat source, and detecting pyroelectric currentgenerated by oscillation with the electronic circuit.

These types of oscillation signal converters can be used in place of thepiezoelectric elements described above, and in addition, differentsignal converters can be used for the excitation of the resonatingportion and for receiving the oscillation from the resonating portionseparately. For example, a piezoelectric converter can be used forexciting, and an electrostatic capacity-type converter for receiving.The arrangement of exciting and receiving devices can be selectedsuitably and conveniently depending on the number of sensing plates. Forexample, when only one sensing plate is used, they can be arranged onthe surface of the sensing plate; when two sensing plates are used, theycan be arranged on both surfaces of the two, or on each surface.

INDUSTRIAL APPLICABILITY

As described above, a mass sensor and a method for mass sensing of thepresent invention, exhibit excellent effects in that change in variousextremely small masses occurring on a diaphragm, that is change in massload on the diaphragm, can be sensed easily and accurately in a shorttime. Therefore, when a catching substance for catching varioussubstances to be sensed is applied to the diaphragm, the mass sensor canbe used as a gas sensor, taste sensor, odor sensor, immune sensor, ormoisture meter, which can sense various chemical substances ormicroorganisms such as bacteria and viruses easily and quickly. Whensuch a catching substance is not applied to the diaphragm, the masssensor can be used as a film thickness meter, viscosity meter, vacuummeter, or thermometer. In addition, when the sensor is used as an immunesensor substituting the dyeing method, an odor sensor, or a tastesensor, the reliability of tests can be improved, because determinationdoes not rely on human sense.

Also, since the mass sensor of the present invention is little affectedby the temperature of the specimen or change in the properties ofmaterials for the mass sensor itself due to the temperature of thespecimen on sensing resonant frequencies, and can measure an extremelysmall quantity of a 0.1 nanogram order as the nature of its structure,it exhibits the effect for sensing an extremely small quantity ofsubstance.

Furthermore, although the mass sensor of the present invention can beused for various applications as described above, since measurement isperformed on the basis of fundamental measurement principle in whichchange in resonant frequencies of the resonating portion including thediaphragm subjected to mass load are measured, a plurality of resonatingportions having different functions can be provided in a mass sensoreasily. Therefore, since the use of a plurality of various discretesensors is not required, the mass sensor of the present invention alsoexcels in economic effects in the reduction of costs for incorporatingthe sensor in the measuring location, for facilities for handling ormeasuring such as measuring instruments, as well as the reduction ofcosts by the integration and the shared use of manufacturing equipments.

1. A method for sensing a mass with a mass sensor in which a side of atleast one diaphragm is joined to a side of a sensing plate so that asurface of said diaphragm is perpendicular to a surface of said sensingplate on which a piezoelectric element is installed, and the other sideof said sensing plate is joined to a sensor substrate, wherein saidpiezoelectric element measures a resonant frequency based on at leastone of: (a) a θ-mode swing oscillation of said diaphragm, wherein saiddiaphragm performs a pendular oscillation centered on an axisperpendicularly passing through a center of a fixed plane defined by thejoining surface of said diaphragm and said sensing plate in a directionperpendicular to a side of said diaphragm and also perpendicular to saidperpendicular axis; (b) a φ-mode swing oscillation of said diaphragm,wherein said diaphragm performs a pendular oscillation centered on saidperpendicular axis, swinging in a direction perpendicular to a side ofsaid diaphragm and also perpendicular to said perpendicular axis and ina direction parallel to the side of said diaphragm; or (c) anoscillation of said diaphragm in the direction of said perpendicularaxis.
 2. A method for sensing a mass with a mass sensor having at leastone piezoelectric element, in which a connection plate is joined to adiaphragm at respective sides thereof, at least one sensing plate isjoined to said connection plate at respective sides thereof in adirection perpendicular to the joining direction of said diaphragm andsaid connection plate, and wherein at least a portion of at least oneside of said connection plate and said sensing plate are joined to aside of a sensor substrate; wherein said piezoelectric element measuresa resonant frequency based on at least one of: (a) a θ-mode swingoscillation of said diaphragm, wherein said diaphragm performs apendular oscillation centered on an axis perpendicularly passing througha center of a fixed plane defined by the joining surface of saidconnection plate and said sensor substrate in a direction perpendicularto a side of said diaphragm and also perpendicular to said perpendicularaxis; or (b) a φ-mode swing oscillation of said diaphragm, wherein saiddiaphragm performs a pendular oscillation centered on said perpendicularaxis, swinging in a direction perpendicular to said side of saiddiaphragm and also perpendicular to said perpendicular axis accompaniedby a swing in a direction parallel to said side of said diaphragm.
 3. Amethod for sensing a mass with a mass sensor having at least onepiezoelectric element, in which an assembly of a diaphragm beingsandwiched between two connection plates by joining at respective sidesthereof is placed across respective side surfaces of a depression oracross a through-hole formed in a sensor substrate, a plurality ofsensing plates are interposed between said respective connection platesand a bottom side of said depression or a side of said through-hole, orbetween said diaphragm and said bottom side of said depression or saidside of said through-hole, in a direction perpendicular to the directionof said respective connection plates sandwiching said diaphragm, whereinsaid piezoelectric element measures a resonant frequency based on atleast one of: (a) a θ-mode swing oscillation of said diaphragm, whereinsaid diaphragm performs a pendular oscillation centered on aperpendicular axis perpendicularly passing through the center of a fixedplane defined by the joining surface of said connection plate and saidsensor substrate in a direction perpendicular to a side of saiddiaphragm and also perpendicular to said perpendicular axis; (b) aφ-mode swing oscillation of said diaphragm, wherein said diaphragmperforms a pendular oscillation centered on said perpendicular axis,swinging in a direction perpendicular to said side of said diaphragm andalso perpendicular to said perpendicular axis accompanied by a swing ina direction parallel to said side of said diaphragm; (c) a swingoscillation of said diaphragm centered on said perpendicular axis,oscillating parallel to a direction perpendicular to said side of saiddiaphragm and also perpendicular to said perpendicular axis; or (d) arotating oscillation of said diaphragm with respect to said surface ofsaid diaphragm.
 4. A mass sensor comprising: a sensor substrate; atleast one connection plate extending along a first direction and havinga first end attached to a first portion of said sensor substrate and anopposed second end; at least one diaphragm attached to said second endof said connection plate; at least one sensing plate arranged in asubstantially parallel planar relationship with respect to said sensorsubstrate, said sensing plate having a first end attached to a secondportion of said sensor substrate and an opposed second end attached toone of said diaphragm and said connection plate; at least onepiezoelectric element arranged on at least a portion of a surface ofsaid sensing plate; wherein said at least one connection plate, said atleast one diaphragm, said at least one sensing plate and said at leastone piezoelectric element define a resonance portion; and means formeasuring a change in the resonant frequency of said resonance portion.